9-溴菲

9-溴菲
英文名	9-Bromophenanthrene
別名	9-溴代菲
識別
CAS號	573-17-1
SMILES	c1c(cccc2)c2c(cccc3)c3c1Br;
性質
化學式	C14H9Br
摩爾質量	257.13 g·mol⁻¹
外觀	白色晶體粉末
密度	1.409 g·cm−3
熔點	63 °C（336 K）
沸點	190 °C（463 K）（1.2 Torr）
溶解性（水）	難溶
溶解性	可溶於乙醇
相關物質
其他陰離子	9-碘菲
相關化學品	9-溴蒽
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

9-溴菲是一種有機化合物，化學式為C₁₄H₉Br，它是溴菲的同分異構體之一。

製備

由於菲在發生親電取代反應時，9位的反應活性最高^[3]，因此可以用溴直接對菲溴化得到。^[4]

N-溴代丁二酰亞胺^[5]或四丁基三溴化銨^[6]也可作為溴化試劑進行反應。

反應

9-溴菲具有鹵代烴的通性，如它和苯硼酸在Pd₂(dba)₃的催化下發生鈴木偶聯反應，生成9-苯基菲；^[7]在CuI-Pd(PPh₃)₂Cl₂的催化下和4-叔丁基苯乙炔發生薗頭偶合反應，生成9-(4-叔丁基苯)乙炔基菲。^[8]它和三苯基膦在苯酚中加熱回流，得到9-菲基三苯基溴化鏻。^[9]它和苯硫酚鈉在N-甲基吡咯烷酮中反應，得到9-甲硫基菲；硒酚鹽可以發生類似反應：^[10]

它在液氨中和氨基鈉發生取代反應，生成9-氨基菲；^[11]它和三(三甲基硅基)硅烷在偶氮二異丁腈的存在下發生還原反應，生成菲。^[12]

它也可以經反應得到金屬有機化合物，如和鎂反應，得到9-菲基溴化鎂^[13]；和正丁基鋰反應，得到9-菲基鋰，^[14]並可通過進一步反應來製備其它金屬有機化合物，如三(9-菲基)銻、三(9-菲基)鉍等^[15]。它和四(三乙基膦)鉑(0)反應，得到溴化-9-菲基二(三乙基膦)鉑^[16]。

用途

9-溴菲可用於有機合成及磷光材料的研究。^[17]^[18]

參考文獻

^ ^1.0 ^1.1 馮美榮, 崔子祥, 薛永強. 合成9-溴菲影響因素的研究. 太原理工大學學報, 2008. 39 (6): 570-572.
^ ^2.0 ^2.1 Buu-Hoi. The halogenation of aromatic and heterocyclic compounds. Justus Liebigs Annalen der Chemie, 1944. 556: 1-9. ISSN: 0075-4617.
^ 湯德祥. 菲親電取代反應活性的探討. 溫州師範學院學報（自然科學版）, 2004. 25 (5):10-13.
^ Nguyen, Thi Thanh Thuy; Guyon, Hélène; Nguyen, Kim Phi Phung; Boussonnière, Anne; Mortier, Jacques; Castanet, Anne-Sophie. Chiral Ligand-Mediated Nucleophilic Aromatic Substitution of Naphthoic Acids: A Fast and Efficient Access to Axially Chiral Biaryls. European Journal of Organic Chemistry. 2020, 2020 (25): 3829–3833. ISSN 1434-193X. doi:10.1002/ejoc.202000317.
^ George, Stephen R. D.; Frith, Thomas D. H.; Thomas, Donald S.; Harper, Jason B. Putting corannulene in its place. Reactivity studies comparing corannulene with other aromatic hydrocarbons. Organic & Biomolecular Chemistry. 2015, 13 (34): 9035–9041. ISSN 1477-0520. doi:10.1039/C5OB01215E.
^ Chaudhuri, Mihir K.; Khan, Abu T.; Patel, Bhisma K.; Dey, Deepa; Kharmawophlang, Wancydora; Lakshmiprabha, T.R.; Mandal, Gagan C. An environmentally benign synthesis of organic ammonium tribromides (OATB) and bromination of selected organic substrates by tetrabutylammonium tribromide (TBATB). Tetrahedron Letters. 1998, 39 (44): 8163–8166. ISSN 0040-4039. doi:10.1016/S0040-4039(98)01818-8.
^ Dai, Wei-Min; Li, Yannain; Zhang, Ye; Wah Lai, Kwong; Wu, Jinlong. A novel class of amide-derived air-stable P,O-ligands for Suzuki cross-coupling at low catalyst loading. Tetrahedron Letters. 2004, 45 (9): 1999–2001. ISSN 0040-4039. doi:10.1016/j.tetlet.2003.12.142.
^ Meng, Lingkui; Fujikawa, Takao; Kuwayama, Motonobu; Segawa, Yasutomo; Itami, Kenichiro. Thiophene-Fused π-Systems from Diarylacetylenes and Elemental Sulfur. Journal of the American Chemical Society. 2016, 138 (32): 10351–10355. ISSN 0002-7863. doi:10.1021/jacs.6b06486.
^ Huang, Wenhua; Zhong, Chun-Hong. Metal-Free Synthesis of Aryltriphenylphosphonium Bromides by the Reaction of Triphenylphosphine with Aryl Bromides in Refluxing Phenol. ACS Omega. 2019, 4 (4): 6690–6696. ISSN 2470-1343. doi:10.1021/acsomega.9b00568.
^ Chan, Shiuh-Chuan; Jang, Jing-Pei; Cherng, Yie-Jia. Microwave-assisted synthesis of substituted phenanthrenes, anthracenes, acenaphthenes, and fluorenes. Tetrahedron. 2009, 65 (10): 1977–1981. ISSN 0040-4020. doi:10.1016/j.tet.2009.01.029.
^ Altiparmakian, R. H.; Braithwaite, R. S. W. A new route to 9-phenanthrylamine. Journal of the Chemical Society C: Organic. 1967: 1818. ISSN 0022-4952. doi:10.1039/j39670001818.
^ Odedra, Arjan; Geyer, Karolin; Gustafsson, Tomas; Gilmour, Ryan; Seeberger, Peter H. Safe, facile radical-based reduction and hydrosilylation reactions in a microreactor using tris(trimethylsilyl)silane. Chemical Communications. 2008, (26): 3025. ISSN 1359-7345. doi:10.1039/b803715a.
^ Kurata, Yuto; Otsuka, Shinya; Fukui, Norihito; Nogi, Keisuke; Yorimitsu, Hideki; Osuka, Atsuhiro. Aromatic Metamorphosis of Dibenzofurans into Triphenylenes Starting with Nickel-Catalyzed Ring-Opening C–O Arylation. Organic Letters. 2017, 19 (6): 1274–1277. ISSN 1523-7060. doi:10.1021/acs.orglett.6b03861.
^ Dent, BR; Halton, B. Studies in the Cycloproparene Series: 1,1-Dichloro-1h-Cyclopropa[l]Phenanthrene. Australian Journal of Chemistry. 1986, 39 (11): 1789. ISSN 0004-9425. doi:10.1071/CH9861789.
^ Lee, Eun Ji; Hong, Jin Seok; Kim, Tae-Jeong; Kang, Youngjin; Han, Eun Me; Lee, Jae Jung; Song, Kihyung; Kim, Dong-Uk. Synthesis and Structural Characterization of Main Group 15 Organometallics R3M and R(Ph)2P(=N-Ar)(M = P, Sb, Bi; R = phenanthrenyl; Ar = 2,6-iPr2-C6H3). Bulletin of the Korean Chemical Society. 2005, 26 (12): 1946–1952. ISSN 0253-2964. doi:10.5012/bkcs.2005.26.12.1946.
^ Raphael Karikachery, Alice; Lee, Han Baek; Masjedi, Mehdi; Ross, Andreas; Moody, Morgan A.; Cai, Xiaochen; Chui, Megan; Hoff, Carl D.; Sharp, Paul R. High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes. Inorganic Chemistry. 2013, 52 (7): 4113–4119. ISSN 0020-1669. doi:10.1021/ic4004998.
^ Mikhailov, B. M.; Chernova, N. G. Phenanthrene series. I. Synthesis of phenanthrene derivatives by means of organolithium compounds. Zhurnal Obshchei Khimii, 1951. 21. 1517-1524. ISSN: 0044-460X.
^ Zhu, Qing; Wang, Hui; Zhao, Xiao Ran; Jin, Wei Jun. The phosphorescent behaviors of 9-bromo- and 9-iodophenanthrene in crystals modulated by π–π interactions, C–H⋯π hydrogen bond and C–I⋯π halogen bond. Journal of Photochemistry and Photobiology A: Chemistry. 2014, 274: 98–107. ISSN 1010-6030. doi:10.1016/j.jphotochem.2013.10.007.

[Feng-1] 1.0 ^1.1 馮美榮, 崔子祥, 薛永強. 合成9-溴菲影響因素的研究. 太原理工大學學報, 2008. 39 (6): 570-572.

[Buu-Hoi-2] 2.0 ^2.1 Buu-Hoi. The halogenation of aromatic and heterocyclic compounds. Justus Liebigs Annalen der Chemie, 1944. 556: 1-9. ISSN: 0075-4617.

[3] 湯德祥. 菲親電取代反應活性的探討. 溫州師範學院學報（自然科學版）, 2004. 25 (5):10-13.

[4] Nguyen, Thi Thanh Thuy; Guyon, Hélène; Nguyen, Kim Phi Phung; Boussonnière, Anne; Mortier, Jacques; Castanet, Anne-Sophie. Chiral Ligand-Mediated Nucleophilic Aromatic Substitution of Naphthoic Acids: A Fast and Efficient Access to Axially Chiral Biaryls. European Journal of Organic Chemistry. 2020, 2020 (25): 3829–3833. ISSN 1434-193X. doi:10.1002/ejoc.202000317.

[5] George, Stephen R. D.; Frith, Thomas D. H.; Thomas, Donald S.; Harper, Jason B. Putting corannulene in its place. Reactivity studies comparing corannulene with other aromatic hydrocarbons. Organic & Biomolecular Chemistry. 2015, 13 (34): 9035–9041. ISSN 1477-0520. doi:10.1039/C5OB01215E.

[6] Chaudhuri, Mihir K.; Khan, Abu T.; Patel, Bhisma K.; Dey, Deepa; Kharmawophlang, Wancydora; Lakshmiprabha, T.R.; Mandal, Gagan C. An environmentally benign synthesis of organic ammonium tribromides (OATB) and bromination of selected organic substrates by tetrabutylammonium tribromide (TBATB). Tetrahedron Letters. 1998, 39 (44): 8163–8166. ISSN 0040-4039. doi:10.1016/S0040-4039(98)01818-8.

[7] Dai, Wei-Min; Li, Yannain; Zhang, Ye; Wah Lai, Kwong; Wu, Jinlong. A novel class of amide-derived air-stable P,O-ligands for Suzuki cross-coupling at low catalyst loading. Tetrahedron Letters. 2004, 45 (9): 1999–2001. ISSN 0040-4039. doi:10.1016/j.tetlet.2003.12.142.

[8] Meng, Lingkui; Fujikawa, Takao; Kuwayama, Motonobu; Segawa, Yasutomo; Itami, Kenichiro. Thiophene-Fused π-Systems from Diarylacetylenes and Elemental Sulfur. Journal of the American Chemical Society. 2016, 138 (32): 10351–10355. ISSN 0002-7863. doi:10.1021/jacs.6b06486.

[9] Huang, Wenhua; Zhong, Chun-Hong. Metal-Free Synthesis of Aryltriphenylphosphonium Bromides by the Reaction of Triphenylphosphine with Aryl Bromides in Refluxing Phenol. ACS Omega. 2019, 4 (4): 6690–6696. ISSN 2470-1343. doi:10.1021/acsomega.9b00568.

[10] Chan, Shiuh-Chuan; Jang, Jing-Pei; Cherng, Yie-Jia. Microwave-assisted synthesis of substituted phenanthrenes, anthracenes, acenaphthenes, and fluorenes. Tetrahedron. 2009, 65 (10): 1977–1981. ISSN 0040-4020. doi:10.1016/j.tet.2009.01.029.

[11] Altiparmakian, R. H.; Braithwaite, R. S. W. A new route to 9-phenanthrylamine. Journal of the Chemical Society C: Organic. 1967: 1818. ISSN 0022-4952. doi:10.1039/j39670001818.

[12] Odedra, Arjan; Geyer, Karolin; Gustafsson, Tomas; Gilmour, Ryan; Seeberger, Peter H. Safe, facile radical-based reduction and hydrosilylation reactions in a microreactor using tris(trimethylsilyl)silane. Chemical Communications. 2008, (26): 3025. ISSN 1359-7345. doi:10.1039/b803715a.

[13] Kurata, Yuto; Otsuka, Shinya; Fukui, Norihito; Nogi, Keisuke; Yorimitsu, Hideki; Osuka, Atsuhiro. Aromatic Metamorphosis of Dibenzofurans into Triphenylenes Starting with Nickel-Catalyzed Ring-Opening C–O Arylation. Organic Letters. 2017, 19 (6): 1274–1277. ISSN 1523-7060. doi:10.1021/acs.orglett.6b03861.

[14] Dent, BR; Halton, B. Studies in the Cycloproparene Series: 1,1-Dichloro-1h-Cyclopropa[l]Phenanthrene. Australian Journal of Chemistry. 1986, 39 (11): 1789. ISSN 0004-9425. doi:10.1071/CH9861789.

[15] Lee, Eun Ji; Hong, Jin Seok; Kim, Tae-Jeong; Kang, Youngjin; Han, Eun Me; Lee, Jae Jung; Song, Kihyung; Kim, Dong-Uk. Synthesis and Structural Characterization of Main Group 15 Organometallics R3M and R(Ph)2P(=N-Ar)(M = P, Sb, Bi; R = phenanthrenyl; Ar = 2,6-iPr2-C6H3). Bulletin of the Korean Chemical Society. 2005, 26 (12): 1946–1952. ISSN 0253-2964. doi:10.5012/bkcs.2005.26.12.1946.

[16] Raphael Karikachery, Alice; Lee, Han Baek; Masjedi, Mehdi; Ross, Andreas; Moody, Morgan A.; Cai, Xiaochen; Chui, Megan; Hoff, Carl D.; Sharp, Paul R. High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes. Inorganic Chemistry. 2013, 52 (7): 4113–4119. ISSN 0020-1669. doi:10.1021/ic4004998.

[17] Mikhailov, B. M.; Chernova, N. G. Phenanthrene series. I. Synthesis of phenanthrene derivatives by means of organolithium compounds. Zhurnal Obshchei Khimii, 1951. 21. 1517-1524. ISSN: 0044-460X.

[18] Zhu, Qing; Wang, Hui; Zhao, Xiao Ran; Jin, Wei Jun. The phosphorescent behaviors of 9-bromo- and 9-iodophenanthrene in crystals modulated by π–π interactions, C–H⋯π hydrogen bond and C–I⋯π halogen bond. Journal of Photochemistry and Photobiology A: Chemistry. 2014, 274: 98–107. ISSN 1010-6030. doi:10.1016/j.jphotochem.2013.10.007.

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