加布里尔伯胺合成反应

加布里尔伯胺合成，是使用酞醯亞胺鉀（琥珀酰亚胺，邻二苯甲酰亚胺）将鹵代烷轉換成一級胺的反应。名稱取自德國化學家西格蒙德·加布里尔（德语：Siegmund Gabriel）。[1][2][3][4]

传统加布里尔合成

加布里尔合成
加布里尔合成

邻苯二甲酰亚胺的鈉鹽或鉀鹽與一級鹵代烷发生亲核取代反應（构型翻转），生成烷基鄰苯二甲醯亞胺。二級鹵代烷無法行此反應。由于邻苯二甲酰亚胺的氮上只有一个氢原子，只能引入一个烷基，故该反应是制取较纯净的一级胺的常用方法。

反应最后用酸处理，使一級胺以成盐的形式纯化。[5]若水解很困难，可以用肼的水溶液或乙醇溶液逆流反應（Ing-Manske法），使取代酞酰亚胺肼解，產生鄰苯二甲醯肼沉澱和一級胺。以上的两种处理方法都有不足，水解法產率低且會伴隨副產物的生成，而肼解法中分離鄰苯二甲醯肼十分麻煩（邻苯二甲酰肼因为水溶性非常好，若产生的胺酯溶性好则非常容易水洗除去，其收率通常可以达到80%以上）。因此還有其他使胺自鄰苯二甲醯亞胺解離的方法。[6]

用加布里尔合成制取氨基酸时，如果直接用α-卤代酸，则酰亚胺盐会与羧酸反应，生成相应的羧酸盐。因此可以用α-卤代酯作原料，将羧基保护，等反应后水解时，酯比酰胺更容易水解，羧基也就自然游离出来。

机理

加布里尔合成机理

第一步是氨基钾盐对于卤代烃的烷基化过程，这个过程是一个SN2反应。第二步，是N-烷基化合物的肼解反应：首先是肼对于羰基的亲核加成，然后是开环和质子转移，接着是分子内的SNAc反应和质子转移，最后是断开了四面体中间态而最终形成的伯胺以及副产物－邻苯二甲酰肼。 [7]

加布里尔替代试剂

现在已经发展了很多能够替代邻苯二甲酰亚胺盐的试剂。比如说，糖精钠盐就是从电性来讲非常类似于邻苯二甲酰亚胺盐的试剂。它的一些优势在于：对于有些底物来讲，它的脱保护更加容易，而对于二级卤代烃来说，它的反应活性更佳，能够补充邻苯二甲酰亚胺对于仲胺合成的不足。[8]

参见

外部链接

参考文献

  1. ^ Gabriel, S. Ueber eine Darstellung primärer Amine aus den entsprechenden Halogenverbindungen. Ber. 1887, 20: 2224 [2009-01-31]. （原始内容存档于2020-04-10）. 
  2. ^ Sheehan, J. C.; Bolhofer, V. A. An Improved Procedure for the Condensation of Potassium Phthalimide with Organic Halides. J. Am. Chem. Soc. 1950, 72: 2786. doi:10.1021/ja01162a527. 
  3. ^ Gibson, M.S.; Bradshaw, R.W. The Gabriel Synthesis of Primary Amines. Angew. Chem. Int. Ed. Engl. 1968, 7: 919. doi:10.1002/anie.196809191. 
  4. ^ Mitsunobu, O. Comp. Org. Syn. 1991, 6, 79-85.（综述）
  5. ^ Khan, M. N. Kinetic Evidence for the Occurrence of a Stepwise Mechanism in the Hydrazinolysis of Phthalimide. J. Org. Chem. 1995, 60: 4536. doi:10.1021/jo00119a035. 
  6. ^ Osby, J. O.; Martin, M. G.; Ganem, B. An Exceptionally Mild Deprotection of Phthalimides. Tetrahedron Lett. 1984, 25 (20): 2093. doi:10.1016/S0040-4039(01)81169-2. 
  7. ^ Khan, M. N. Suggested Improvement in the Ing-Manske Procedure and Gabriel Synthesis of Primary Amines: Kinetic Study on Alkaline Hydrolysis of N-Phthaloylglycine and Acid Hydrolysis of N-(o-Carboxybenzoyl)glycine in Aqueous Organic Solvents. J. Org. Chem. 1996, 61, 8063-8068.
  8. ^ Ulf Ragnarsson, Leif Grehn (1991). "Novel Gabriel Reagents". Acc. Chem. Res. 24: 285–289

Read other articles:

نادي اتحاد مانشستر

نادي اتحاد مانشستر تأسس عام 2005  الملعب غيغ لين  البلد المملكة المتحدة  الدوري دوري الشمال الممتاز  [لغات أخرى]‏  الموقع الرسمي الموقع الرسمي  الطقم الرسمي الطقم الأساسي الطقم الاحتياطي الطقم الثالث تعديل مصدري - تعديل   نادي اتحاد مانشستر لكرة القدم (...

 

Sepak bola di Jepang

Sepak bola di Jepangpemain Jubilo Iwata dan penggemarnya merayakan gol di Piala J.League pada tahun 2010NegaraJepangBadan yang mengaturAsosiasi Sepak Bola JepangTim nasionaltim nasional priatim nasional wanitaKompetisi nasional Piala KaisarKompetisi klub J LeagueKompetisi internasional Piala AFC Liga Champions AFC Piala Dunia FIFA Piala Asia Sepak bola adalah olahraga terkenal kedua di Jepang,[1][2] setelah Baseball.[3] Asosiasi Sepak Bola Jepang, mengelola liga sepak...

 

Cité de Carcassonne

Medieval citadel of Carcassonne, France You can help expand this article with text translated from the corresponding article in French. (September 2013) Click [show] for important translation instructions. View a machine-translated version of the French article. Machine translation, like DeepL or Google Translate, is a useful starting point for translations, but translators must revise errors as necessary and confirm that the translation is accurate, rather than simply copy-pasting machi...

Luisa María Alcalde Luján

Mexican politician In this Spanish name, the first or paternal surname is Alcalde and the second or maternal family name is Luján. Luisa María Alcalde LujánSecretary of the InteriorIncumbentAssumed office 19 June 2023PresidentAndrés Manuel López ObradorPreceded byAlejandro Encinas Rodríguez (Acting)Secretary of LaborIn office1 December 2018 – 19 June 2023PresidentAndrés Manuel López ObradorPreceded byRoberto CampaSucceeded byMarath BolañosFederal DeputyIn offic...

 

Willamette Stone

Historic surveying marker in Oregon, US The Willamette Stone's location is now commemorated by a circular marker and plaque. Close up of the current marker The Willamette Stone is located where the meridian and baseline intersect on this BLM map. The Willamette Stone was a small stone obelisk originally installed by the Department of Interior in 1885 in the western hills of Portland, Oregon in the United States to mark the intersection and origin of the Willamette meridian and Willamette base...

 

Thomas G. Gentry

American ornithologist and writer Thomas George GentryBornFebruary 28, 1843Holmesburg, Philadelphia, Pennsylvania, U.S.Died1905Occupation(s)Ornithologist, writer Thomas George Gentry (February 28, 1843 – 1905) was an American educator, ornithologist, naturalist and animal rights writer. Gentry authored an early work applying the term intelligence to plants. Biography Gentry was born in Holmesburg area of Philadelphia.[1] In 1861, he entered the profession of teaching in Philadelphia...

Шахри-Сухте

Объект всемирного наследия ЮНЕСКО[* 1]Shahr-i Sokhta[* 2] Страна  Иран Тип Культурный Критерии ii, iii, iv Ссылка 1456 Регион[* 3] Объекты ЮНЕСКО в Азии Включение 2014 год (38-я сессия) ↑ Название в официальном рус. списке ↑ Название в официальном англ. списке ↑ Регион по класси...

 

Bricqueville-la-Blouette

Ne doit pas être confondu avec Bricqueville-sur-Mer. Bricqueville-la-Blouette L'église Saint-Martin. Administration Pays France Région Normandie Département Manche Arrondissement Coutances Intercommunalité Communauté de communes Coutances Mer et Bocage Maire Mandat Rodolphe Jardin 2020-2026 Code postal 50200 Code commune 50084 Démographie Gentilé Bricquevillais Populationmunicipale 535 hab. (2021 ) Densité 86 hab./km2 Géographie Coordonnées 49° 02′ 03″...

 

羅德島州

本條目存在以下問題，請協助改善本條目或在討論頁針對議題發表看法。 此條目需要擴充。 (2013年1月1日)请協助改善这篇條目，更進一步的信息可能會在討論頁或扩充请求中找到。请在擴充條目後將此模板移除。 此條目需要补充更多来源。 (2013年1月1日)请协助補充多方面可靠来源以改善这篇条目，无法查证的内容可能會因為异议提出而被移除。致使用者：请搜索一下条目的...

2016年美國總統選舉

2016年美國總統選舉 ← 2012 2016年11月8日 2020 → 538個選舉人團席位獲勝需270票民意調查投票率55.7%[1][2] ▲ 0.8 %   获提名人 唐納·川普 希拉莉·克林頓 政党 共和黨 民主党 家鄉州 紐約州 紐約州 竞选搭档 迈克·彭斯 蒂姆·凱恩 选举人票 304[3][4][註 1] 227[5] 胜出州/省 30 + 緬-2 20 + DC 民選得票 62,984,828[6] 65,853,514[6]...

 

تيرنس تاو

تيرنس تاو Terence Chi-Shen Tao معلومات شخصية الميلاد 17 يوليو 1975 (العمر 48 سنة)أديليد، جنوب أستراليا الإقامة لوس أنجلوس، كاليفورنيا الجنسية أسترالي[1] أمريكي[1] عضو في الجمعية الملكية،  والأكاديمية الوطنية للعلوم،  والأكاديمية الأمريكية للفنون والعلوم،  والأكاديمية �...

 

محمد بن سلمان آل سعود

صاحب السمو الملكي الأمير محمد بن سلمانبن عبد العزيز آل سعود محمد بن سلمان في 2019 ولي العهد في المنصب21 يونيو 20176 سنواتٍ و10 أشهرٍ و27 يومًا – حتى الآن محمد بن نايف بن عبد العزيز آل سعود   ولي العهد ورئيس مجلس الوزراء في المنصب27 سبتمبر 2022سنةً واحدةً و7 أشهرٍ و21 يومًا – حتى...

Baby boom

Period marked by a significant increase of birth rate This article is about the concept of a baby boom. For the post-WWII baby boom, see Mid-20th century baby boom. For other uses, see Baby boom (disambiguation). A baby boom is a period marked by a significant increase of births. This demographic phenomenon is usually ascribed within certain geographical bounds of defined national and cultural populations. The cause of baby booms involves various fertility factors. The best-known baby boom oc...

 

Montana (Bulgarie)

Cet article est une ébauche concernant une localité bulgare. Vous pouvez partager vos connaissances en l’améliorant (comment ?) selon les recommandations des projets correspondants. Pour les articles homonymes, voir Montana (homonymie). Montana Монтана Héraldique Administration Pays Bulgarie Oblast Montana Maire Zlatko Jivkov (Indépendant) Code postal 3400 Démographie Population 39 595 hab. (en 2017) Géographie Coordonnées 43° 25′ 00″ nord,...

 

IBM PCjr

Home computer 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: IBM PCjr – news · newspapers · books · scholar · JSTOR (April 2023) (Learn how and when to remove this message) IBM PCjrIBM PCjr with original chiclet keyboard, PCjr color display, and 64 KB memory expansion cardManufacturerTeledyne, Lewisbur...

Spa Conference (29 September 1918)

The Spa conference of September 29, 1918 is the last important conference between the main political and military leaders of the Reich,[n 1] then engaged in the First World War. Held in the last weeks of the conflict, it is intended to draw the political and military conclusions of the Bulgarian defection. Indeed, after the failures encountered by the central powers in Italy and on the Western Front, the leaders of the Reich can only acknowledge the strategic impasse in which they hav...

 

David Donoho

American statistician David L. DonohoDonoho at the ICM 2018Born (1957-03-05) March 5, 1957 (age 67)Los Angeles, California, United StatesNationalityAmericanAlma materHarvard University (BA)Princeton University (PhD)AwardsShaw Prize (2013)Gauss Prize (2018)Scientific careerFieldsStatisticsInstitutionsStanford University University of California, BerkeleyDoctoral advisorPeter J. HuberDoctoral studentsEmmanuel CandèsJianqing Fan David Leigh Donoho (born March 5, 1957) is an American ...

 

Alabama

U.S. state This article is about the U.S. state. For the river, see Alabama River. For other uses, see Alabama (disambiguation). State in the United StatesAlabamaState FlagSealNicknames: the Yellowhammer State, the Heart of Dixie, the Cotton StateMotto(s): Latin: Audemus jura nostra defendere(We dare defend our rights)Anthem: AlabamaMap of the United States with Alabama highlightedCountryUnited StatesBefore statehoodAlabama TerritoryAdmitted to the UnionDecember 14, 1819 (22nd)Capit...

1860

Este artículo o sección necesita referencias que aparezcan en una publicación acreditada. Busca fuentes: «1860» – noticias · libros · académico · imágenesEste aviso fue puesto el 26 de noviembre de 2020. Año 1860Años 1857 • 1858 • 1859 ← 1860 → 1861 • 1862 • 1863Decenios Años 1830 • Años 1840 • Años 1850 ← Años 1860 → Años 1870 • Años 1880 • Años 1890Siglos Siglo XVIII ← Siglo XIX → Siglo XXTabla anual del sig...

 

Jade Bight

Bay on Germany's North Sea coast Map showing Jade Bay (Jadebusen) at lower center Development of the Jade Bight and the interim Weser delta:• blue areas = advancement of waterbodies• green areas = growth of land• grayish pale blue areas = sometimes flooded• grayish lilac areas = newly gained land lost again• grayish pink areas = regained land lost again• brown to red lines = dikes• bold intensive light blue line = today's coastline• light blue lines = today's limit of mudflats...