JP2019522668A - 芳香族フッ素化の方法 - Google Patents
芳香族フッ素化の方法 Download PDFInfo
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- OGTSHGYHILFRHD-UHFFFAOYSA-N O=C(c1ccccc1)c(cc1)ccc1F Chemical compound O=C(c1ccccc1)c(cc1)ccc1F OGTSHGYHILFRHD-UHFFFAOYSA-N 0.000 description 1
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N [O-][N+](c(cc1)ccc1C(c1ccccc1)=O)=O Chemical compound [O-][N+](c(cc1)ccc1C(c1ccccc1)=O)=O ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B39/00—Halogenation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C49/215—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/18—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Quinoline Compounds (AREA)
Abstract
Description
本出願は、2016年7月15日出願の米国仮出願第62/362,725号に対する優先権の利益を主張するものであり、その開示全体が本明細書に組み込まれる。
次いで混合物を、式Ar−Fを有する化学種を生成するのに十分な条件下で反応させ、その後、所望の生成物を単離してもよい。
数字が示されていない場合(例えば、アリール−アルキル−)、炭素数1〜12のアルキルが考えられる。好ましいアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、sec−ブチル、tert−ブチル、ペンチル、ヘキシルおよびtert−オクチルが含まれるが、これらに限定されない。
特に断りのない限り、アリール基は、本明細書に記載の合成に適合できる1個または複数の置換基で任意に選択して置換される。
そのような置換基は、以下を含むが、これらに限定されない。
スルホネート基、
ホウ素含有基、
アルキル基、
ニトロ基、
ハロゲン、
シアノ基、
−C(O)RA(式中、RAはヒドロキシ、アルキル、アルコキシ、アリール、アリールオキシ、ヘテロアリール、ヘテロアリールオキシ、アミノ、またはモノ−もしくはジ(アルキルアミノ)を表す)、
−NRNC(O)RM(式中、RNはHまたはアルキルであり、RMはアルキル、アリール、またはヘテロアリールである)、
C2〜C8アルケニル、および
他の芳香族基。
ヘテロアリール環は1個または複数のヘテロアリール環、芳香族もしくは非芳香族炭化水素環、またはヘテロシクロアルキル環に縮合、またはそうでなければ結合してもよい。 ヘテロアリール基の例は、ピリジニル、ピリミジニル、ピリダジニル、ピロリル、トリアジニル、イミダゾリル、トリアゾリル、フラニル、チエニル、オキサゾリル、およびチアゾイルを含むが、これらに限定されない。ヘテロアリール基は、本明細書に記載の合成に適合できる1個または複数の置換基で、任意に選択して置換されてもよい。
そのような置換基は、以下を含むが、これらに限定されない。
フルオロスルホネート基、
スルホネート基、
ホウ素含有基、
アルキル基、
ニトロ基、
ハロゲン、
シアノ基、
−C(O)RA(式中、RAはヒドロキシ、アルキル、アルコキシ、アリール、アリールオキシ、ヘテロアリール、ヘテロアリールオキシ、アミノ、または、モノ−もしくはジ(アルキルアミノ)を表す)、
−NRNC(O)RM(式中RNはHまたはアルキルであり、RMはアルキル、アリール、またはヘテロアリールである)、
C2〜C8アルケニル、および
他の芳香族基
Ar−X+フッ素化試薬+TMA(Oar)→Ar−F (スキームI)
nは0または1、2、3、4、もしくは5であり、
ZはOまたはSを表し、
各R1は独立してC1〜C6アルキル、C2〜C6アルケニル、ニトロ、ハロ、シアノ、CO2R2(式中、各R2は水素、C1〜C6アルキル、アミノ、(C1〜C6アルキル)アミノ、またはジ(C1〜C6アルキル)アミノである)、アリール、またはヘテロアリールを表す。
nは0であり、ZはSまたはOであり、
nは1であり、ZはSまたはOであり、R1はメチルであり、
nは2であり、ZはSまたはOであり、各R1はメチルである
化合物を含む。
一実施形態では、反応混合物はフッ素化試薬、例えばフッ化スルフリル4当量を含有する。
他の実施形態では、反応混合物はテトラアルキルアンモニウムフェノレート塩2〜3当量を含有する。
一例では、反応混合物はテトラアルキルアンモニウムフェノレート塩2.5当量を含有する。
これらの当量は、反応混合物中の芳香族化合物Ar−Xのモル量に対して計算される。
Claims (10)
- 溶媒を反応混合物へ供給するステップ、
フッ素化試薬を前記反応混合物へ供給するステップ、
式Ar−X
(Aはアリール、置換アリール、ヘテロアリールまたは置換ヘテロアリールであり、
XはCl、Br、IまたはNO2である)
を有する化合物を前記反応混合物へ供給するステップ、
テトラアルキルアンモニウムフェノレート塩を前記反応混合物へ供給するステップ、および
式Ar−Fを有する化学種を生成するのに十分な条件下で反応させるステップ
を含む、フッ素化方法。 - 前記溶媒が、極性非プロトン性溶媒である、請求項1に記載のフッ素化方法。
- Aが、5−クロロ−6−フェニルピコリン酸イソプロピル、2−クロロキノリン、または(4−ニトロフェニル)(フェニル)メタノンである、請求項1または2に記載のフッ素化方法。
- 反応温度が0〜130℃である、請求項1〜3のいずれか一項に記載のフッ素化方法。
- 前記反応混合物が、前記Ar−Xを1当量、テトラメチルアンモニウム2,6−ジメチルフェノレートを2〜3当量、前記フッ素化試薬を3〜10当量を含む、請求項1〜4のいずれか一項に記載のフッ素化方法。
- 前記極性非プロトン性溶媒が、DMF、NMP、DMSO,DMPU、またはDMACを含む、請求項2〜5のいずれか一項に記載のフッ素化方法。
- 前記反応温度が25〜130℃である、請求項4に記載のフッ素化方法。
- 前記テトラアルキルアンモニウムフェノレート塩が、テトラメチルアンモニウム2,6−ジメチルフェノレートである、請求項1〜7のいずれか一項に記載のフッ素化方法。
- 前記反応混合物が触媒を含有しない、請求項1〜8のいずれか一項に記載のフッ素化方法。
- 前記フッ素化試薬が、フッ化スルフリル、アリールフルオロスルホネート、またはヘテロアリールフルオロスルホネートである、請求項1〜9のいずれか一項に記載のフッ素化方法。
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---|---|---|---|
US201662362725P | 2016-07-15 | 2016-07-15 | |
US62/362,725 | 2016-07-15 | ||
PCT/US2017/041889 WO2018013782A1 (en) | 2016-07-15 | 2017-07-13 | Method for aromatic fluorination |
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JP2019522668A true JP2019522668A (ja) | 2019-08-15 |
JP6941155B2 JP6941155B2 (ja) | 2021-09-29 |
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US (1) | US11059782B2 (ja) |
EP (1) | EP3484851B1 (ja) |
JP (1) | JP6941155B2 (ja) |
KR (1) | KR102411819B1 (ja) |
CN (1) | CN109641845B (ja) |
BR (1) | BR112019000620B1 (ja) |
ES (1) | ES2824551T3 (ja) |
WO (1) | WO2018013782A1 (ja) |
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JPH09150516A (ja) * | 1995-11-28 | 1997-06-10 | Kyocera Corp | インクジェットヘッド |
PT2046396E (pt) * | 2006-07-18 | 2013-12-09 | Univ Nebraska | Agentes de fluoração anidro 18f radioactivamente marcados e métodos para a sua produção e utilização |
WO2011008725A2 (en) * | 2009-07-13 | 2011-01-20 | Massachusetts Institute Of Technology | Metal-catalyzed carbon-fluorine bond formation |
CN103596931B (zh) | 2011-04-12 | 2016-10-12 | 哈佛大学校长及研究员协会 | 有机化合物的氟化 |
FR2975990B1 (fr) * | 2011-06-01 | 2013-05-24 | Rhodia Operations | Procede de preparation d'un compose organique fluore |
WO2013188554A1 (en) | 2012-06-12 | 2013-12-19 | The Regents Of The University Of California | Fluorination of aryl compounds |
CN105693661A (zh) * | 2014-12-15 | 2016-06-22 | 苏州旺山旺水生物医药有限公司 | (2S,3R,4R)-3,5-二取代-2-脱氧-2-羟基-2-甲基-D-核糖-γ-内酯的制备方法及其中间体 |
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- 2017-07-13 WO PCT/US2017/041889 patent/WO2018013782A1/en unknown
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Publication number | Publication date |
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KR20190028497A (ko) | 2019-03-18 |
CN109641845B (zh) | 2023-01-13 |
EP3484851A1 (en) | 2019-05-22 |
US11059782B2 (en) | 2021-07-13 |
US20190292152A1 (en) | 2019-09-26 |
BR112019000620A2 (pt) | 2019-04-24 |
EP3484851B1 (en) | 2020-09-02 |
KR102411819B1 (ko) | 2022-06-22 |
ES2824551T3 (es) | 2021-05-12 |
WO2018013782A1 (en) | 2018-01-18 |
BR112019000620B1 (pt) | 2022-10-11 |
CN109641845A (zh) | 2019-04-16 |
JP6941155B2 (ja) | 2021-09-29 |
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