巴尔托利吲哚合成

巴尔托利吲哚合成（Bartoli indole synthesis），又称巴尔托利反应，指从邻取代的芳香硝基化合物与乙烯基格氏试剂制备取代吲哚。[1][2][3][4]

巴尔托利吲哚合成
巴尔托利吲哚合成

底物硝基邻位无取代基时，反应一般不能发生。通常用三倍量的格氏试剂，确保产率。

这个方法是制备7-取代吲哚的较好方法。[5][6]

类似的反应还有Leimgruber-Batcho吲哚合成，但巴尔托利吲哚合成的优点在于这个反应可以在碳环和杂环上都引入取代基。

反应机理

以邻硝基甲苯(1)与丙烯基格氏试剂(2)生成3,7-二甲基吲哚(13)的反应为例：[7]

巴尔托利吲哚合成
巴尔托利吲哚合成

首先格氏试剂与硝基芳烃加成为中间体(3)。(3)自发分解为亚硝基芳烃(4)和醇镁(5)。(5)在反应最后酸化时可以转化为羰基化合物(6)。(4)则与第二分子格氏试剂加成为中间体(7)，邻位取代基的位阻引发(7)的[3,3]-σ迁移反应，使其转变为(8)。(8)发生分子内亲核加成，环合，再经芳构化得到(10)。(10)再与第三分子的格氏试剂作用，生成羟基二氢吲哚的镁盐(12)。最后酸化，(12)水解，消除一分子水，得到吲哚衍生物(13)。

可见，三分子格氏试剂的作用分别是：一分子在第二步被消除，最终转化为羰基化合物(6)；一分子与氮上的氢发生交换，生成烯烃(11)；一分子成为吲哚环的C-2和C-3。

反应中的亚硝基芳烃中间体(4)可以分离出来。它与两分子格氏试剂反应，也可得到吲哚，说明它是反应的中间体。

变体

多布斯改进法

阿德里安·多布斯用邻位的溴作定位基成环，反应后再用偶氮二异丁腈和三丁基锡烷将溴除去，生成7-位无取代基的吲哚。[8]

多布斯改进法
多布斯改进法

参见

参考资料

  1. ^ Bartoli, G.; Palmieri, G.; Bosco, M.; Dalpozzo, R. The reaction of vinyl grignard reagents with 2-substituted nitroarenes: A new approach to the synthesis of 7-substituted indoles. Tetrahedron Lett. 1989, 30: 2129–2132. doi:10.1016/S0040-4039(01)93730-X. )
  2. ^ Bartoli, G.; Bosco, M.; Dalpozzo, R.; Palmieri, G.; Marcantoni, E. Reactivity of nitro- and nitroso-arenes with vinyl grignard reagents: synthesis of 2-(trimethylsilyl)indoles. J. Chem. Soc., Perkin Trans. 1. 1991, 1: 2757–2761. doi:10.1039/p19910002757. 
  3. ^ Dobbs, A. P.; Voyle, M.; Whitall, N. Synthesis of Novel Indole Derivatives: Variations in the Bartoli Reaction. Synlett. 1999, 1999: 1594–1596. doi:10.1055/s-1999-2900. 
  4. ^ Dalpozzo, R.; Bartoli, G. Bartoli Indole Synthesis (PDF). Curr. Org. Chem. 2005, 9: 163–178 [2009-09-23]. doi:10.2174/1385272053369204. （原始内容 (PDF)存档于2007-09-28）. 
  5. ^ Dobson, D.; Todd, A.; Gilmore, J. The Synthesis of 7-Alkoxyindoles. Synth. Commun. 1991, 21: 611–617. doi:10.1080/00397919108020827. 
  6. ^ Dobson, D. R.; Gilmore, J.; Long, D. A. Synthesis of 7-Formylindole Using the Bartoli Indole Methodology. Synlett. 1992, 1992: 79–80. doi:10.1055/s-1992-21273. 
  7. ^ Bosco, M.; Dalpozzo, R.; Bartoli, G.; Palmieri, G.; Petrini, M. J. Chem. Soc. Perkin Trans. 2 1991, 657-663.
  8. ^ Dobbs, A. Total Synthesis of Indoles from Tricholoma Species via Bartoli/Heteroaryl Radical Methodologies. J. Org. Chem. 2001, 66: 638–641. doi:10.1021/jo0057396. 

Read other articles:

Bobby Darin

Bobby DarinDarin pada tahun 1959Informasi latar belakangNama lahirWalden Robert CassottoLahir(1936-05-14)14 Mei 1936AsalThe Bronx, New York, Amerika SerikatGenreBig band, rock and roll, pop tradisional, folkPekerjaanPenyanyi-penulis lagu, aktorInstrumenVokal, gitar, piano, drum, harmonika, xylophoneTahun aktif1956–1973LabelDecca, Atco, Capitol, Brunswick, Atlantic, Motown Walden Robert Casotto atau lebih dikenal dengan nama Bobby Darin (14 Mei 1936 – 20 Desember 1973), merup...

 

جوزيف بلاك

جوزيف بلاك (بالإنجليزية: Joseph Black)‏[1]    معلومات شخصية الميلاد 16 أبريل 1728 [2][3][4][5][6]  بوردو[7]  الوفاة 6 ديسمبر 1799 (71 سنة) [5]  إدنبرة[7]  مواطنة مملكة بريطانيا العظمى[1]  عضو في الجمعية الملكية للكيمياء،  والجمعية الملكي...

 

British Aerospace Jetstream

Jetstream Jenis Pesawat penumpang regional Pembuat British Aerospace Penerbangan perdana 28 Maret 1980 Diperkenalkan 29 Juni 1982 Status Aktif, tidak diproduksi Pengguna utama Pascan AviationLinks Air Angkatan Udara Arab Saudi Dibuat 1980-1993 Jumlah 386 Dikembangkan dari Handley Page Jetstream Varian British Aerospace Jetstream 41 British Aerospace Jetstream adalah sebuah pesawat terbang sipil berukuran kecil bermesin turboprop ganda, dengan lambung dengan kabin bertekanan, dikembangka...

イスラームにおける結婚

イスラームにおける結婚（イスラームにおけるけっこん）とは、二者の間で行われる法的な契約である。新郎新婦は自身の自由な意思で結婚に同意する。口頭または紙面での規則に従った拘束的な契約は、イスラームの結婚で不可欠だと考えられており、新郎と新婦の権利と責任の概要を示している[1]。イスラームにおける離婚は様々な形をとることができ、個�...

 

Grob G103 Twin Astir

German two-seat glider, 1976 This article includes a list of general references, but it lacks sufficient corresponding inline citations. Please help to improve this article by introducing more precise citations. (December 2012) (Learn how and when to remove this template message) G 103 Twin Astir G103 Twin Astir landing Role SailplaneType of aircraft National origin Germany Manufacturer Grob Aircraft First flight 31 December 1976 Number built 291 The Grob G 103 Twin Astir is a glass-reinforce...

 

Progress 20

Soviet unmanned Progress cargo spacecraft Progress 20A Progress 7K-TG spacecraftMission typeSalyut 7 resupplyCOSPAR ID1984-038A SATCAT no.14932[1] Spacecraft propertiesSpacecraftProgress (No.121)Spacecraft typeProgress 7K-TG[2]ManufacturerNPO Energia Start of missionLaunch date15 April 1984, 08:12:53 UTC[1]RocketSoyuz-U2[2]Launch siteBaikonur, Site 31/6 End of missionDisposalDeorbitedDecay date7 May 1984, 00:32:51 UTC[3] Orbital parametersReference ...

World Surf League

Governing body for professional surfers This article needs to be updated. The reason given is: some portions contain current information from 2015. Please help update this article to reflect recent events or newly available information. (August 2020) World Surf LeagueCurrent season, competition or edition: 2024 World Surf LeagueSportProfessional SurfingFounded2013CountriesInternationalHeadquartersSanta Monica, CaliforniaMost recentchampion(s) Filipe Toledo (men)(2nd title) Caroline Marks (wom...

 

Tomographie en cohérence optique

Image OCT d'un sarcome Pour les articles homonymes, voir OCT. La tomographie en cohérence optique[1] ou tomographie optique cohérente (TCO ou (en) OCT) est une technique d'imagerie médicale bien établie qui utilise une onde lumineuse pour capturer des images tridimensionnelles d'un matériau qui diffuse la lumière (par exemple un tissu biologique), avec une résolution de l'ordre du micromètre (1 µm). La tomographie en cohérence optique est basée sur une technique interférométrique...

 

Mikoyan-Gurevich MiG-21

Mikoyan-Gurevich MiG-21Un MiG-21 Lancer-C rumeno in volo.DescrizioneTipocaccia intercettorecacciabombardiere Equipaggio1 ProgettistaArtëm Ivanovič MikojanMichail Iosifovič Gurevič Costruttore OKB 155 Data primo volo14 febbraio 1955 Data entrata in servizio1959 Utilizzatore principale V-VS Esemplarioltre 10 000 Dimensioni e pesiTavole prospettiche Lunghezza14,77 m Apertura alare7,16 m Altezza4,1 m Superficie alare23 m² Peso a vuoto4 600 kg Peso max al decollo8 750 kg Capaci...

Флора Армении

Дикая пшеница Эребунийского заповедника — Пшеница араратская (Triticum araraticum) Армения занимает одно из первых мест в мире по количеству видов растений на единицу площади — свыше 100 видов на 1 км²[1]. Разнообразие растительности республики обусловлено наличием слож�...

 

2022–23 Persian Gulf Pro League

40th season of top-tier football league in Iran Football league seasonPersian Gulf Pro LeagueSeason2022–23Dates2 October 2022 (2 October 2022) — 18 May 2023 (18 May 2023)ChampionsPersepolis 8th Pro League title15th Iranian titleRelegatedNaft MISMes KermanChampions LeaguePersepolisSepahanNassajiTractorMatches played240Goals scored480 (2 per match)Top goalscorerShahriyar Moghanlou (13 Goals)Biggest home winEsteghlal 7–1 Tractor (18 May 2023)Biggest away winNaft Masjed sole...

 

Partai Bansa Dayak Sarawak

Parti Bansa Dayak SarawakSarawak Dayak People's PartyPBDS Ketua umumDatuk Amar Dr. Leo Moggie Anak IrokDibentuk17 Juli 1983Dibubarkan5 Desember 2003 (pertama) 21 Oktober 2004 (kedua)Kantor pusatKuchingPolitik MalaysiaPartai politikPemilihan umum Malaysia Artikel ini adalah bagian dari seri Politik dan KetatanegaraanMalaysia Pemerintahan federal Konstitusi Malaysia Hak asasi manusia Hukum Kontrak sosial Rukun Negara Monarki Yang di-Pertuan Agong Ibrahim Iskandar dari Johor Majelis Raja-Raja Le...

San Matteo (Genoa)

Roman Catholic church in Genoa, Liguria, Italy Church of Saint Matthew(Chiesa di San Matteo)The façade of the Basilica.ReligionAffiliationRoman CatholicProvinceGenoaEcclesiastical or organizational statusNational monumentStatusActiveLocationLocationGenoa, ItalyGeographic coordinates44°24′29.60″N 8°55′58.90″E / 44.4082222°N 8.9330278°E / 44.4082222; 8.9330278ArchitectureTypeChurchStyleGothicCompleted1125 San Matteo is a Roman Catholic church in Genoa, in th...

 

1992–93 Kentucky Wildcats men's basketball team

1992–93 season of University of Kentucky men's basketball team 1992–93 Kentucky Wildcats men's basketballSEC tournament championsNCAA tournament, Final FourConferenceSoutheastern ConferenceRankingCoachesNo. 3APNo. 2Record30–4 (13–3 SEC)Head coachRick Pitino (4th season)Assistant coaches Herb Sendek Billy Donovan Bernadette Locke-Mattox Home arenaRupp ArenaSeasons← 1991–921993–94 → 1992–93 Southeastern Conference men's basketball standing...

 

2010 Nevada gubernatorial election

See also: 2010 United States gubernatorial elections 2010 Nevada gubernatorial election ← 2006 November 2, 2010 2014 →   Nominee Brian Sandoval Rory Reid Party Republican Democratic Popular vote 382,350 298,170 Percentage 53.36% 41.61% County results Sandoval:      40–50%      50–60%      60–70%      70–80% Governor before election Jim Gibbons Republican...

Beorhtwulf of Mercia

9th-century King of the Mercians Not to be confused with Beowulf. BeorhtwulfPenny of BeorhtwulfLegend: ber(ht)vlf rexKing of MerciaReign840–852 ADPredecessorWiglafSuccessorBurgredDied852 ADConsortSæthrythIssueBeorhtricBeorhtfrith Beorhtwulf (Old English: [ˈbeorˠxtwuɫf], meaning bright wolf; also spelled Berhtwulf; died 852) was King of Mercia, a kingdom of Anglo-Saxon England, from 839 or 840 to 852. His ancestry is unknown, though he may have been connected to Beornwulf, who ru...

 

Ashburn Alley

Ashburn Alley, Citizens Bank Park, Philadelphia, named after Baseball Hall of Famer Richie Ashburn Ashburn Alley is the open concourse behind center field at Citizens Bank Park, home of the Philadelphia Phillies. It is named after Hall of Famer Richie Ashburn, Phillies center fielder from 1948 to 1959, and was also a long time broadcaster for the Phillies from 1963 until his death in September 1997. Ashburn Alley spans from the left field gate to The Yard kids area, and features a street-fair...

 

سكان إيران

طهران، العاصمة الإيرانية والمدينة الأکثر کثافة سکانية في إيران مشهد، المدينة الثانية من حيث الکثافة السکانية في إيران اصفهان، المدينة الثالثة من حيث الکثافة السکانية في إيران كرج، المدينة الرابعة من حيث الکثافة السکانية في إيران تبريز، المدينة الخامسة من حيث الکثافة ال�...

Ekaterina Tkachenko

Russian alpine skier (born 1995) Yekaterina TkachenkoTkachenko in 2016Country RussiaFull nameYekaterina Igorevna TkachenkoBorn (1995-03-07) 7 March 1995 (age 29)Harare, Zimbabwe Medal record Representing  Russia Winter Universiade 2019 Krasnoyarsk Slalom 2019 Krasnoyarsk Giant slalom 2019 Krasnoyarsk Parallel team event Yekaterina Igorevna Tkachenko (‹See Tfd›Russian: Екатери́на И́горевна Ткаче́нко; born 7 March 1995 in Harare) is a Zimbabwe...

 

Manuel Tuñón de Lara

Spanish historian Manuel Tuñón de LaraTuñón de Lara in 1982Born(1915-09-08)8 September 1915MadridDied25 January 1997(1997-01-25) (aged 81)LejonaAlma materUniversidad de MadridOccupation(s)Historian and professorEmployers University of Pau and Pays de l'Adour Universidad de las Islas Baleares Universidad del País Vasco Political party Unión de Juventudes Comunistas de España Juventudes Socialistas Unificadas AwardsGran Cruz de la Orden Civil de Alfonso X el Sabio (1996) Manuel...