ビルスマイヤー・ハック反応

ビルスマイヤー・ハック反応（ビルスマイヤー・ハックはんのう、英: Vilsmeier–Haack reaction）またはビルスマイヤー反応[1][2] はオキシ塩化リン (POCl3) の存在下、アミドと活性芳香族化合物の間で起こる有機化学反応である。この反応で重要なのはイミンであり、これがプロトン化された芳香族ケトンまたはアルデヒドを与える。例えば、ベンズアニリドとジメチルアニリンはオキシ塩化リンの存在下で非対称なジアリールケトンを生成する[3]。またアントラセンは9位の炭素が選択的にホルミル化される[4]。

反応機構

反応機構

アミドとオキシ塩化リンの反応で求電子的なイミニウムイオンが生成する。これが弱い求電子剤となり求電子芳香族置換反応によりイミン中間体を形成する。これが容易に加水分解され最終生成物であるアリールケトンやアリールアルデヒドを生成する。

応用例

この反応の最近の応用例の一つとして、これまでの方法では収率が16%しかなかった、トリフェニルアミンを原料とするトリス（4-ホルミルフェニル）アミンの新しい合成法が挙げられる[5]。この低収率の原因は、他の2つのベンゼン環に存在していたイミン基が残ったベンゼン環を不活性化し、3つ目のホルミル化反応を進行しにくくしていることであった。新しい方法ではジイミン体を加水分解によりジホルミル体とし、最後に残ったベンゼン環を再びホルミル化することで、95% の収率でトリス（4-ホルミルフェニル）アミンを得ている。

脚注

  1. ^ Vilsmeier, A.; Haack, A. (1927). “Über die Einwirkung von Halogenphosphor auf Alkyl-formanilide. Eine neue Methode zur Darstellung sekundärer und tertiärer p-Alkylamino-benzaldehyde”. Chem. Ber. 60: 119-122. doi:10.1002/cber.19270600118. 
  2. ^ E. Campaigne and W. L. Archer (1953). "p-Dimethylaminobenzaldehyde". Organic Syntheses (英語). 33: 27.; Collective Volume, vol. 4, p. 331
  3. ^ Charles D. Hurd and Carl N. Webb (1927). "p-Dimethylaminobenzophenone". Organic Syntheses (英語). 7: 24.; Collective Volume, vol. 1, p. 217
  4. ^ (A) L. F. Fieser, J. L. Hartwell, J. E. Jones, (B) J. H. Wood, and R. W. Bost (1940). "9-Anthraldehyde; 2-Ethoxy-1-naphthaldehyde". Organic Syntheses (英語). 20: 11.; Collective Volume, vol. 3, p. 98
  5. ^ Mallegol, T.; Gmouh, S.; Meziane, M. A. A.; Blanchard-Desce, M.; Mongin, O. (2005). “Practical and Efficient Synthesis of Tris(4-formylphenyl)amine, a Key Building Block in Materials Chemistry”. Synthesis: 1771-1774. doi:10.1055/s-2005-865336. 

関連項目

Read other articles:

Lake Placid, New York

For the body of water, see Lake Placid (New York). Village in New York, United StatesLake Placid, New YorkVillageLake Placid from McKenzie MountainNickname: The Olympic VillageLocation in Essex County and the state of New York.Coordinates: 44°17′08″N 073°59′07″W / 44.28556°N 73.98528°W / 44.28556; -73.98528CountryUnited StatesStateNew YorkCountyEssexTownNorth ElbaGovernment • TypeCouncil / Manager • MayorArt DevlinArea[1]...

 

Yusuf al-Qaradawi

Artikel ini perlu dikembangkan agar dapat memenuhi kriteria sebagai entri Wikipedia.Bantulah untuk mengembangkan artikel ini. Jika tidak dikembangkan, artikel ini akan dihapus. الجهمي (en) Yusuf al-Qaradawi(2006) Nama dalam bahasa asli(ar) يُوسُف القرضاوي BiografiKelahiran9 September 1926 Saft Turab (en) Kematian26 September 2022 (96 tahun)Doha  1r Leader of the International Union of Muslim Scholars (en) 2004 – 7 November 2018 ← tanpa nila...

 

Estella Warren

Estella WarrenWarren saat syuting film Blue Seduction pada November 2008.LahirEstella Dawn Warren23 Desember 1978 (umur 45)Peterborough, Ontario, KanadaTempat tinggalLos Angeles, California, ASKebangsaanKanadaPendidikanSilverthorn Collegiate InstitutePekerjaan Aktris model perenang Tahun aktif2001–sekarangTinggi5 ft 9 in (1,75 m) Estella Dawn Warren (lahir 23 Desember 1978)[1] adalah seorang aktris, model fesyen dan mantan perenang asal Kanada. Pada masa ka...

James Mattis

James Mattis Menteri Pertahanan Amerika Serikat ke-26Masa jabatan20 Januari 2017 – 1 Januari 2019PresidenDonald TrumpWakilRobert O. WorkPatrick M. Shanahan PendahuluAsh CarterPenggantiMark EsperKomandan Komando Pusat Amerika Serikat ke-11Masa jabatan11 Agustus 2010 – 22 Maret 2013PresidenBarack Obama PendahuluDavid PetraeusPenggantiLloyd AustinKomandan Komando Pasukan Gabungan Amerika Serikat ke-5Masa jabatan9 November 2007 – 11 Agustus 2010PresidenGeorge ...

 

Rimini Calcio 1964-1965

Questa voce sull'argomento stagioni delle società calcistiche italiane è solo un abbozzo. Contribuisci a migliorarla secondo le convenzioni di Wikipedia. Segui i suggerimenti del progetto di riferimento. Voce principale: Associazione Calcio Rimini 1912. Rimini CalcioStagione 1964-1965Sport calcio Squadra Rimini Allenatore Romolo Bizzotto Presidente Guido Belardinelli Serie C12º posto nel girone B. Maggiori presenzeCampionato: Nanni (33) Miglior marcatoreCampionato: Benetti, Mant...

 

Football Club Castiglione 2012-2013

Questa voce sull'argomento stagioni delle società calcistiche italiane è solo un abbozzo. Contribuisci a migliorarla secondo le convenzioni di Wikipedia. Segui i suggerimenti del progetto di riferimento. Voce principale: Football Club Castiglione Società Sportiva Dilettantistica. Football Club CastiglioneStagione 2012-2013Sport calcio SquadraFootball Club Castiglione Allenatore Lorenzo Ciulli Presidente Tiziano Tonello Lega Pro Seconda Divisione7º posto nel girone A. Maggiori presen...

Corney Grain

British entertainer Richard Corney GrainRichard Corney Grain, 1880sBorn(1844-10-26)26 October 1844TevershamDied16 March 1895(1895-03-16) (aged 50)LondonOccupation(s)entertainer, songwriter Richard Corney Grain (26 October 1844 – 16 March 1895), known by his stage name Corney Grain, was an entertainer and songwriter of the late Victorian era. Biography Corney Grain (left) and Alfred German Reed (right) portrayed in Entr'acte in 1895, the year they both died Born at Teversham in Cambridg...

 

UEFA–CAF Meridian Cup

Football tournamentUEFA-CAF Meridian CupOrganising bodyUEFA & CAFFounded1997Abolished2007RegionEuropeAfricaLast championsEuropean Selection U-18Most successful team(s) Spain (3 titles) The UEFA–CAF Meridian Cup was a football tournament that featured national teams from Europe and Africa among players under 18, and was part of the co-operation programme between UEFA and the CAF. Meridian Project The UEFA–CAF Meridian Cup was part of the Meridian Project, a co-operation agreement concl...

 

Il... Belpaese

1977 Italian filmIl... BelpaeseDirected byLuciano SalceWritten byCastellano & Pipolo Luciano Salce Paolo VillaggioProduced byFulvio LucisanoStarringPaolo Villaggio Silvia DionisioCinematographyEnnio GuarnieriEdited byAntonio SicilianoMusic byGianni BoncompagniPiergiorgio FarinaPaolo OrmiRelease date 1977 (1977) Running time115 minutesCountryItalyLanguageItalian Il... Belpaese (Italian for The... Beautiful Country) is a 1977 black comedy film written and directed by Luciano Salce and ...

Grand Palais (Constantinople)

Pour les articles homonymes, voir Grand Palais. Grand palaisΜέγα ΠαλάτιονVestige du Palais de Boucoléon, qui faisait partie du Palais SacréPrésentationType PalaisCivilisation Empire byzantinDestination initiale Résidence des basileusStyle Architecture byzantineÉtat de conservation démoli ou détruit (d)LocalisationPays Empire byzantinCommune ConstantinopleCoordonnées 41° 00′ 23″ N, 28° 58′ 40″ E Géolocalisation sur la carte : T...

 

Válvula hidráulica

Válvula disipadora de energía tipo Howell-Bunger. Una válvula hidráulica es un mecanismo que sirve para regular el flujo de fluidos.[1]​ Las válvulas que se utilizan en obras hidráulicas son un caso particular de válvulas industriales ya que presentan algunas características únicas y por tanto merecen ser tratadas de forma separada. Clasificación La clasificación de las válvulas utilizadas en las obras hidráulicas puede hacerse según el tipo de obra hidráulica: Presas y c...

 

Disciplina (divinità)

Questa voce o sezione sull'argomento mitologia non cita le fonti necessarie o quelle presenti sono insufficienti. Puoi migliorare questa voce aggiungendo citazioni da fonti attendibili secondo le linee guida sull'uso delle fonti. Segui i suggerimenti del progetto di riferimento. Nella mitologia romana, Disciplina era una divinità minore, personificazione della disciplina. La stessa parola disciplina, un nome latino, ha molte sfaccettature di significato. Si riferisce all'istruzione, al...

Messier 69

Messier 69M69 difoto dari Hubble Space Telescope; 3.5′ Kredit: NASA/STScI/WikiSkyData pengamatan (J2000 epos)KelasV[1]Rasi bintangSagittariusAsensio rekta 18j 31m 23.10d[2]Deklinasi −32° 20′ 53.1″[2]Jarak29.7 ribu tcMagnitudo tampak (V)+8.31[3]Dimensi tampak (V)9′.8Karakteristik fisikRadius42 tc[4]MetalisitasTemplat:Fe/H dexPerkiraan umur13.06  Miliar tahun[5]Nama lainM69, NGC 6637, GCl 96[3]...

 

كمية

  لمعانٍ أخرى، طالع كمية (توضيح). كميةمعلومات عامةصنف فرعي من خاصيةقيمة جانب من جوانب قياس مجال الدالة مجموعة صورة الدالة مجموعة الأعداد الحقيقية ممثلة بـ مستوى القياسquantity value (en) بعد الكمية المادية النقيض خاصية جودة تعديل - تعديل مصدري - تعديل ويكي بيانات الكمية (بالإن...

 

لوس بوزويلوس دي كالاترافا (سيوداد ريال)

  لوس بوزويلوس دي كالاترافا (بالإسبانية: Pozuelos de Calatrava, Los)‏[1]   - بلدية -    لوس بوزويلوس دي كالاترافا (سيوداد ريال)  خريطة الموقع تقسيم إداري البلد إسبانيا  [2] المقاطعة مقاطعة ثيوداد ريال خصائص جغرافية إحداثيات 38°54′04″N 4°10′10″W / 38.90111111111...

The Killing Field

2014 Australian thriller television film The Killing FieldThe Killing Field logoWritten byMichaeley O'BrienSarah SmithDirected bySamantha LangStarringRebecca GibneyChloe BorehamLiam McIntyrePeter O'BrienCountry of originAustraliaOriginal languageEnglishProductionProducersBill HughesSarah SmithRebecca GibneyCinematographyToby Oliver[1]Running time90 minutesOriginal releaseNetworkSeven Network[2]Release4 May 2014 (2014-05-04) The Killing Field is an Australian mys...

 

Petr Pála

Czech tennis player and coach Petr PálaPetr Pála after the 2016 Fed Cup finalCountry (sports) Czech RepublicResidencePrague, Czech RepublicBorn (1975-10-02) 2 October 1975 (age 48)Prague, CzechoslovakiaHeight1.93 m (6 ft 4 in)Turned pro1993PlaysRight-handed (two-handed backhand)Prize money$1,106,011SinglesCareer record0–1Career titles0 0 Challenger, 0 FuturesHighest ranking286 (24 June 1996)Grand Slam singles resultsUS OpenQ1 (1996)Doubles...

 

Czechoslovakia men's national basketball team

This article is about the men's team. For the women's team, see Czechoslovakia women's national basketball team. This article needs additional citations for verification. Please help improve this article by adding citations to reliable sources. Unsourced material may be challenged and removed.Find sources: Czechoslovakia men's national basketball team – news · newspapers · books · scholar · JSTOR (September 2014) (Learn how and when to remove this mes...

Devin Wenig

American business executive Devin WenigDevin WenigBornDevin Norse Wenig1966 (age 57–58)Flatbush, Brooklyn, New York, USEducationUnion College (BA) Columbia Law School (JD)OccupationBusiness executiveTitleFormer CEO, eBayTermJuly 2015 - September 2019PredecessorJohn DonahoeSuccessorScott Schenkel (interim) Jamie IannoneBoard member ofGeneral Motors (2018-) eBay (2011–2019) Reuters (2006–11)SpouseCindy Lee Horowitz Devin Norse Wenig (born 1966)[1] is an American busi...

 

Carl Sagan

Carl SaganSagan pada tahun 1980Lahir(1934-11-09)9 November 1934Brooklyn, New York, ASMeninggal20 Desember 1996(1996-12-20) (umur 62)Seattle, Washington, U.S.Tempat tinggalIthaca, New York, U.S.[butuh rujukan]KebangsaanAmerika SerikatAlmamaterUniversitas ChicagoDikenal atasSearch for Extra-Terrestrial Intelligence (SETI)Cosmos: A Personal VoyageVoyager Golden RecordPioneer plaqueContactPenghargaanOersted Medal (1990)NASA Distinguished Public Service Medal (dua kali)Pulitzer Prize...