Nitroalken

Nitroalken yoki nitro olefin, uning tarkibiy qismlari, alken va nitroguruhlarning funksionalligini birlashtirgan funktsional guruh boʻlib, alkenlarni faollashtirish orqali oʻzining kimyoviy xususiyatlarini namoyon qiladi va funktsional guruhni Maykl reaktsiyasi yoki Diels-Alder qo'shimchalari kabi maxsus reaktsiyalarda foydali qiladi.

Sintez

Nitroalkenlar turli yoʻllar bilan sintezlanadi, diqqatga sazovor misollar:

Genri reaktsiyasi kabi nitroaldol reaktsiyalari :^[1]^[2]^[3]^[4]

Kumush nitrit va elementar yoddan in-situ hosil boʻlgan nitril yodid bilan alkenni nitrlash :^[5]

Kislotali sharoitda alkenlarni azot oksidi va alyuminiy oksidi katalizatori bilan bevosita nitrlash:^[6]

Alkenlarni Clayfen bilan toʻgʻridan-toʻgʻri nitrlash ( Montmorillonit loyida qoʻllab-quvvatlanadigan temir (III) nitrat ):^[7]

Nitro-spirtlarning suvsizlanishi:^[8]

Reaksiyalar

Nitroalkenlar turli xil kimyoviy funktsiyalar uchun foydali vositadir.

Likoritsidin sintezida oʻzini Maykl akseptori sifatida tutadigan nitroalken:^[1]^[9]

Nitroalken Diels-Alder siklo yuklanishida butadienga nisbatan faollashtirilgan dienofil vazifasini bajaradi:^[1]^[10]

Barton-Zard reaksiyasi orqali pirol hosilalarining sintezi:^[11]

Nitroalkenning indol hosil qiluvchi peritsiklik reaksiyasi :^[12]

Gidroksilamin funktsional guruhiga ega boʻlgan alkenga qisman gidrogenlash :^[13]

Birlamchi aminlarga qaytarilishi :^[13]^[14]

Asimmetrik Stetter reaktsiyasi :^[15]

Manbalar

↑ ^1,0 ^1,1 ^1,2 Furniss, Brian. Vogel's Textbook of Practical Organic Chemistry 5th Ed.. London: Longman Science & Technical, 1996 — 635, 768, 1035–1036, & 1121-bet. ISBN 9780582462366.
↑ Ballini, Roberto; Castagnani, Roberto; Petrini, Marino (1992). "Chemoselective synthesis of functionalized conjugated nitroalkenes". The Journal of Organic Chemistry 57 (7): 2160–2162. doi:10.1021/jo00033a045.
↑ Worrall, David E. (1929). "Nitrostyrene". Org. Synth. 9: 66. doi:10.15227/orgsyn.009.0066.
↑ Chandrasekhar, S.; Shrinidhi, A. (2014). "Useful Extensions of the Henry Reaction: Expeditious Routes to Nitroalkanes and Nitroalkenes in Aqueous Media". Synthetic Communications 44 (20): 3008–3018. doi:10.1080/00397911.2014.926373.
↑ Waldman, Steve; Monte, Aaron, Monte; Bracey, Ann; Nichols, David (1996). "One-pot Claisen rearrangement/O-methylation/alkene isomerization in the synthesis of ortho-methoxylated phenylisopropylamines". Tetrahedron Letters 37 (44): 7889–7892. doi:10.1016/0040-4039(96)01807-2.
↑ Mukaiyama, T.; Hata E.; Yamada, T. (1995). "Convenient and Simple Preparation of Nitroolefins Nitration of Olefins with Nitric Oxide". Chemistry Letters 24 (7): 505–506. doi:10.1246/cl.1995.505.
↑ Varma, Rajender; Naicker, Kannan; Liesen, Per (1998). "Selective nitration of styrenes with clayfen and clayan: A solvent-free synthesis of β-nitrostyrenes". Tetrahedron Letters 39 (23): 3977–3980. doi:10.1016/S0040-4039(98)00740-0.
↑ Ranganathan, Darshan; Rao, Bhushan; Ranganathan, Subramania; Mehrotra, Ashok; Iyengar, Radha (1980). "Nitroethylene: a stable, clean, and reactive agent for organic synthesis". The Journal of Organic Chemistry 45 (7): 1185–1189. doi:10.1021/jo01295a003.
↑ Jubert, Carole; Knochel, Paul (1992). "Preparation of polyfunctional nitro olefins and nitroalkanes using the copper-zinc reagents RCu(CN)ZnI". The Journal of Organic Chemistry 57 (20): 5431–5438. doi:10.1021/jo00046a027.
↑ Noboru Ono; Hideyoshi Miyake; Akio Kamimura; Aritsune, Kaji (1987). "Regioselective Diels–Alder reactions. The nitro group as a regiochemical control element". Perkin Transactions 1: 1929–1935. doi:10.1039/P19870001929.
↑ Jie Jack Li. Heterocyclic Chemistry in Drug Discovery. New York: Wiley, 2013. ISBN 9781118354421. pp.43-4
↑ Novellino, Luisa; d'Ischia, Marco; Prota, Giuseppe (1999). "Expedient Synthesis of 5,6-Dihydroxyindole and Derivatives via an Improved Zn(II)-Assisted 2,β-Dinitrostyrene Approach". Synthesis 1999 (5): 793–796. doi:10.1055/s-1999-3469. https://archive.org/details/sim_synthesis_1999-05_5/page/793.
↑ ^13,0 ^13,1 Masahiko Kohno; Shigehiro Sasao; Shun-Ichi Murahashi (1990). "Synthesis of Phenethylamines by Hydrogenation of β-Nitrostyrenes". Bulletin of the Chemical Society of Japan 63 (4): 1252–1254. doi:10.1246/bcsj.63.1252. https://archive.org/details/sim_bulletin-of-the-chemical-society-of-japan_1990-04_63_4/page/1252.
↑ Koch, Werner; Reichert, Benno (1935). "Über die katalytische Hydrierung substituierter ω-Nitrostyrole". Archiv der Pharmazie 273 (18–20): 265–274. doi:10.1002/ardp.19352731802.
↑ DiRocco, D. A.; Oberg, K. M.; Dalton, D. M.; Rovis, T. (2009). "Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity". Journal of the American Chemical Society 131 (31): 10872–10874. doi:10.1021/ja904375q. PMID 19722669. PMC 2747345. //www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=2747345.

[Vogel-1] 1,0 ^1,1 ^1,2 Furniss, Brian. Vogel's Textbook of Practical Organic Chemistry 5th Ed.. London: Longman Science & Technical, 1996 — 635, 768, 1035–1036, & 1121-bet. ISBN 9780582462366.

[2] Ballini, Roberto; Castagnani, Roberto; Petrini, Marino (1992). "Chemoselective synthesis of functionalized conjugated nitroalkenes". The Journal of Organic Chemistry 57 (7): 2160–2162. doi:10.1021/jo00033a045.

[3] Worrall, David E. (1929). "Nitrostyrene". Org. Synth. 9: 66. doi:10.15227/orgsyn.009.0066.

[4] Chandrasekhar, S.; Shrinidhi, A. (2014). "Useful Extensions of the Henry Reaction: Expeditious Routes to Nitroalkanes and Nitroalkenes in Aqueous Media". Synthetic Communications 44 (20): 3008–3018. doi:10.1080/00397911.2014.926373.

[5] Waldman, Steve; Monte, Aaron, Monte; Bracey, Ann; Nichols, David (1996). "One-pot Claisen rearrangement/O-methylation/alkene isomerization in the synthesis of ortho-methoxylated phenylisopropylamines". Tetrahedron Letters 37 (44): 7889–7892. doi:10.1016/0040-4039(96)01807-2.

[6] Mukaiyama, T.; Hata E.; Yamada, T. (1995). "Convenient and Simple Preparation of Nitroolefins Nitration of Olefins with Nitric Oxide". Chemistry Letters 24 (7): 505–506. doi:10.1246/cl.1995.505.

[7] Varma, Rajender; Naicker, Kannan; Liesen, Per (1998). "Selective nitration of styrenes with clayfen and clayan: A solvent-free synthesis of β-nitrostyrenes". Tetrahedron Letters 39 (23): 3977–3980. doi:10.1016/S0040-4039(98)00740-0.

[8] Ranganathan, Darshan; Rao, Bhushan; Ranganathan, Subramania; Mehrotra, Ashok; Iyengar, Radha (1980). "Nitroethylene: a stable, clean, and reactive agent for organic synthesis". The Journal of Organic Chemistry 45 (7): 1185–1189. doi:10.1021/jo01295a003.

[9] Jubert, Carole; Knochel, Paul (1992). "Preparation of polyfunctional nitro olefins and nitroalkanes using the copper-zinc reagents RCu(CN)ZnI". The Journal of Organic Chemistry 57 (20): 5431–5438. doi:10.1021/jo00046a027.

[10] Noboru Ono; Hideyoshi Miyake; Akio Kamimura; Aritsune, Kaji (1987). "Regioselective Diels–Alder reactions. The nitro group as a regiochemical control element". Perkin Transactions 1: 1929–1935. doi:10.1039/P19870001929.

[Li-11] Jie Jack Li. Heterocyclic Chemistry in Drug Discovery. New York: Wiley, 2013. ISBN 9781118354421. pp.43-4

[12] Novellino, Luisa; d'Ischia, Marco; Prota, Giuseppe (1999). "Expedient Synthesis of 5,6-Dihydroxyindole and Derivatives via an Improved Zn(II)-Assisted 2,β-Dinitrostyrene Approach". Synthesis 1999 (5): 793–796. doi:10.1055/s-1999-3469. https://archive.org/details/sim_synthesis_1999-05_5/page/793.

[Masahiko-13] 13,0 ^13,1 Masahiko Kohno; Shigehiro Sasao; Shun-Ichi Murahashi (1990). "Synthesis of Phenethylamines by Hydrogenation of β-Nitrostyrenes". Bulletin of the Chemical Society of Japan 63 (4): 1252–1254. doi:10.1246/bcsj.63.1252. https://archive.org/details/sim_bulletin-of-the-chemical-society-of-japan_1990-04_63_4/page/1252.

[14] Koch, Werner; Reichert, Benno (1935). "Über die katalytische Hydrierung substituierter ω-Nitrostyrole". Archiv der Pharmazie 273 (18–20): 265–274. doi:10.1002/ardp.19352731802.

[15] DiRocco, D. A.; Oberg, K. M.; Dalton, D. M.; Rovis, T. (2009). "Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity". Journal of the American Chemical Society 131 (31): 10872–10874. doi:10.1021/ja904375q. PMID 19722669. PMC 2747345. //www.pubmedcentral.nih.gov/articlerender.fcgi?tool=pmcentrez&artid=2747345.

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