БРОМИРОВАНИЕ АРОМАТИЧЕСКИХ АМИНОВ
Аннотация
Учитывая, что антипирены, биологически активные вещества (противоопухолевые, антибактериальные, противогрибковые, противовирусные), фармакологические препараты, полученные, в частности, на основе бромсодержащих ароматических соединений, широко используются в промышленности и пользуются повышенным спросом, целью данной работы являлось обобщение и систематизация накопленных в этой области знаний. В статье были представлены методы, а также системы реагентов, используемые при бромировании ароматических аминов. Представлено бромирование ароматических аминов агентами галогенирования - бромистым водородом, бромидом натрия, бромидом калия, бромидом аммония, бромидом меди (II), N-бромсукцинимидом, N-бромсахарином, поддерживаемыми полимерами, и различия этих методов с точки зрения используемого окислителя, среды и растворителя, катализатора, региоселективности, количества атомов брома в полученном продукте. Показано влияние растворителей, катализаторов, природы (электронодонорной или электроноакцепторной) и положения (орто-, мета-, пара-) заместителей в ароматическом кольце, условий реакции, молярного соотношения реагентов, температуры реакции и времени проведения реакции бромирования ароматических аминов. Описаны направления реакций бромирования ароматических аминов в различных растворителях, в условиях отсутствия растворителей, в твердых состояниях. Изучено бромирование ароматических аминов в условиях термического, микроволнового, ультрафиолетового излучения. В статье показано региоселективное монобромирование, и также получение ди-, трибромопроизводных ароматических аминов. Также отмечены некоторые экологически безопасные методы бромирования ароматических аминов. Учитывая вышеуказанное, по нашему мнению, данные, представленные в этой статье, будут способствовать оптимизации получения бромпроизводных ароматических аминов, применяемых в промышленности, технике и технологии. <span style="opacity: 0;"> . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </span>
Литература
Jenkner H., Strang R. Patent DE 2813845 A1. 1979.
Jenkner H., Strang R. Patent DE 3014972 A1. 1981
Vyas P.V., Bhatt A.K., Ramachandraiah G., Bedekar A.V. Environmentally benign chlorination and bromina-tion of aromatic amines, hydrocarbons and naphthols. Tet-rahed. Lett. 2003. V. 44. N 21. P. 4085−4088. DOI: 10.1016/S0040-4039(03)00834-7.
Sharma S.K., Agarwal D.D. Molybdate-catalyzed oxida-tive bromination of aromatic compounds using mineral ac-ids and H2O2. Internat. J. Sci. Res. Publ. 2014. V. 4. N 6. P. 1-12.
Liu C., Dai R., Yao G., Deng Y. Selective bromination of pyrrole derivatives, carbazole and aromatic amines with DMSO/HBr under mild conditions. J. Chem. Res. 2014. V. 38. N 10. P. 593-596. DOI: 10.3184/174751914X14114780483352.
Khosravia K., Kazemib S. Green, mild and efficient bromination of aromatic compounds by HBr promoted by trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane in water as a solvent. Chin. Chem. Lett. 2012. V. 23. N 4. P. 387–390. DOI: 10.1016/j.cclet.2012.01.009.
Adimurthy S., Ramachandraiah G., Bedekar A.V., Ghosh S., Ranu B.C., Ghosh P. K. Eco-friendly and ver-satile brominating reagent prepared from a liquid bromine precursor. Royal Soc. Chem. Green Chem. 2006. V. 10. N 8. P. 916-922. DOI: 10.1039/b606586d.
Adibi H., Hajipour A.R., Hashemi M. A convenient and regioselec-tive oxidative bromination of electron rich aromatic rings using potas-sium bromide and benzyltriphenylphosphonium peroxymonosul-fate under nearly neutral reaction conditions. Tetrahed. Lett. 2007. V. 48. N 7. P. 1255−1259. DOI: 10.1016/j.tetlet.2006.12.033.
Tajik H., Shirini F., Hassan-zadeh P., Rashtabadi H.R. Bromina-tion of aromatic compounds with potassium bromide in the presence of poly(4-vinylpyridine)-supported bromate in nonaqueous solution. Synth. Commun. 2005. V. 35. N 14. P. 1947-1952. DOI: 10.1002/chin.200548043.
Hou J., Li Z., Jia X.-D., Lui Z.-Q. Bromination of arenes using I2O5 – KBr in water. Synth. Commun. 2014. V. 44. N 2. P. 181-187. DOI: 10.1080/00397911.2013.796523.
Khazaei A., Zolfigol M.A., Koukabi N., Soltani H., Ba-yani L.S., Kolvari E. Electrophilic bromination of al-kenes, alkynes, and aromatic amines with iodic ac-id/potassium bromide under mild conditions. Synth. Com-mun. 2010. V. 40. N 19. P. 2954-2962. DOI: 10.1080/00397910903349992.
Yousefi-Seyf J., Tajeian K., Kolvari E., Koukabi N., Khazaei A., Zolfigol M.A. A green protocol for the bromination and iodination of the aromatic compounds using H5IO6/NaBr and H5IO6/NaI in the wa-ter. Bull. Korean Chem. Soc. 2012. V. 33. N 8. P. 2619-2622. DOI: 10.5012/bkcs.2012.33.8.2619.
Lee K.-J., Cho H.K., Song C.-E. Bromination of activated arenes by oxone and sodium bromide. Bull. Korean Chem. Soc. 2002. V. 23. N 5. P. 773-775. DOI: 10.5012/bkcs.2002.23.5.773.
Roche D., Prasad K., Repic O., Blacklock T.J. Mild and regiose-lective oxidative bromination of anilines using potassium bromide and sodium perborate. Tetrahed. Lett. 2000. V. 41. N 13. P. 2083-2085. DOI: 10.1016/S0040-4039(00)00119-2.
Fujita M., Leveque J.-M., Komatsu N., Kimura T. Sono-bromination of aromatic compounds based on the ultra-sonic advanced oxidation processes. Ultrason. Sonochem. 2015. V. 27. P. 247-251. DOI: 10.1016/j.ultsonch.2015.04.030.
Raju T., Kulangiappar K., Anbu Kulandainathan M., Uma U., Malini R., Muthukumaran A. Site directed nu-clear bromination of aromatic compounds by an electro-chemical method. Tetrahed. Lett. 2006. V. 47. N 27. P. 4581−4584. DOI: 10.1016/j.tetlet.2006.04.152.
Halder J. An elegant and cost-effective method of aro-matic bromination using sodium bromide and household bleach. RASAYAN J. Chem. 2012. V. 5. N 2. P. 183-185.
Sharma S.K., Agarwal D.D. NH4Br - Br2 Catalysed oxi-dative bromination of aromatic compounds. J. Agricult. Life Sci. 2014. V. 1. N 1. P. 65-81.
Naresh N., Kumar M.A., Reddy M.M., Swamy P., Nanubolu J.B., Narender N. Fast and efficient bromina-tion of aromatic compounds with ammonium bromide and oxone. Synthesis. 2013. V. 45. N 11. P. 1497-1504. DOI: 10.1055/s-0033-1338431.
Krishna Mohan K.V.V., Narender N., Srinivasu P., Kul-karni S.J., Raghavan K.V. Novel bromination method for anilines and anisoles using NH4Br/H2O2 in CH3COOH. Synth. Commun. 2004. V. 34. N 12. P. 2143-2152. DOI: 10.1081/SCC-120038491.
Bhatt S., Nayak S.K. Copper (II) bromide: a simple and selective monobromination reagent for electron-rich aro-matic compounds. Synth. Commun. 2007. V. 37. N 8. P. 1381-1388. DOI: 10.1080/00908320701230026.
Wang H., Wen K., Nurahmat N., Shao Y., Zhang H., Wei C., Li Y., Shen Y., Sun Z. Regioselective chlorination and bromination of unprotected anilines under mild condi-tions using copper halides in ionic liquids. Beilstein J. Org. Chem. 2012. V. 8. N 1. P. 744-748. DOI: 10.3762/bjoc.8.84.
Li X.-L., Wu W., Fan X.-H., Yang L.-M. A facile, regioselective and controllable bromination of aromatic amines using a CuBr2/Oxone system. RSC Adv. 2013. N 30. P. 12091-12095. DOI: 10.1039/C3RA41664J.
Chhattise P.K., Ramaswamy A.V., Waghmode S.B. Regioselec-tive, photochemical bromination of aromatic compounds using N-bromosuccinimide. Tetrahedron Letters. 2008. V. 49. N 1. P. 189−194. DOI: 10.1016/j.tetlet.2007.10.126.
Das B., Venkateswarlu K., Majhi A., Siddaiah V., Reddy K.R. A facile nuclear bromination of phenols and anilines using NBS in the presence of ammonium acetate as a cata-lyst. J. Mol. Catal. A: Chem. 2007. V. 267. N 1-2. P. 30-33. DOI: 10.1016/j.molcata.2006.11.002.
Ganguly N.C., De P., Dutta S. Mild regioselective mono-bromination of activated aromatics and heteroaromatics with N-bromosuccinimide in tetrabutylammonium bro-mide. Synthesis. 2005. V. 7. N 7. P. 1103-1108. DOI: 10.1055/s-2005-861866.
Sarma J.A.R.P., Nagaraju A. Solid state nuclear bromin-ation with N-bromosuccinimide. Part 1. Experimental and theoretical studies on some substituted aniline, phenol and nitro aromatic compounds. J. Chem. Soc., Perkin Trans. 2. 2000. N 6. P. 1113-1118. DOI: 10.1039/A905466I.
Ghaffar A., Jabbar A., Sıddıq M. N-Bromosuccinimide-silica gel: a selective monobromination reagent for aromatic amines and phenols. J. Chem. Soc. Pak. 1994. V. 16. N 4. P. 272-274.
Baharfar .R, Alinezhad.H, Azimi.S, Salehian.F. Regioselective and high-yielding bromination of phenols and anilins using N-bromosaccharin and amberlyst-15. J. Chil. Chem. Soc. 2011. V. 56. N 4. P. 863-865. DOI: 10.4067/S0717-97072011000400008.
Alinezhad H., Tavakkoli S.M., Salehian F. Efficient, rapid, and regioselective bromination of phenols and anilines with N-bromosaccharin using tungstophosphoric acid as a heterogeneous re-cyclable catalyst. Synth. Commun. 2010. V. 40. N 21. P. 3226-3232. DOI: 10.1080/00397910903395268
Alineshad H., Tavakkoli S.M. Directed efficient and rapid bromination of phenols and anilines with N-Bromosaccharin using tungstophosphoric acid as a hetero-geneous recyclable catalyst under solvent-free conditions. Iran. J. Org. Chem. 2010. V. 2. N 3. P. 417-422.
Zarchi M.A.K., Mousavi S.Z. Diazotization-bromination of aromatic amines using polymer-supported bromide via Sandmeyer-type reaction. Journal of Polymer Research. 2014. V. 21. N 1. P. 1-9. DOI: 10.1007/s10965-013-0330-2.
Zarchi M.A.K., Mousavi Z. Diazotization-bromination of aromatic amines using polymer-supported nitrite ion pro-moted by cuprous bromide in water (Sandmeyer type reac-tion). The 16-th İranian chem. Congr. September 7-9. 2013. P. 626.
Verma S., Jain S.L. Complexation of KBr3 with poly(Ethylene Glycol):efficient bromination of aromatics under solvent-less conditions. Org. Chem. Cur. Res. 2012. V. 1. N 2. DOI: 10.4172/2161-0401.1000105.
Mokhtary M., Lakouraj M.M. Polyvinylpolypyrrolidone-bromine complex: mild and efficient polymeric reagent for bromination of activated aromatic compounds. Chin. Chem. Lett. 2011. V. 22. N 1. P. 13-17. DOI: 10.1016/j.cclet.2010.06.002.
Chretien J.-M., Zammattio F., Grognec E.L., Paris M., Cahingt B., Montavon G., Quintard J.-P. Polymer-supported organotin rea-gents for regioselective halogenations of aromatic amines. J. Org. Chem. 2005. V. 70. N 7. P. 2870-2873. DOI: 10.1021/jo0480141.
Ghorbani-Vaghei R., Jalili H. Mild and regioselective bromination of aromatic compounds with N,N,N’,N’-tetrabromobenzene-1,3-disulfonylamide and poly(N-bromobenzene-1,3-disulfonylamide). Synthesis. 2005. P. 1099-1102. DOI: 10.1055/s-2005-861851.
Mishra A.K., Nagarajaiah H., Moorthy J.N. Trihaloisocyanuric acids as atom-economic reagents for halogenation of aromatics and carbonyl compounds in the solid state by ball milling. Eur. J. Org. Chem. 2015. N 12. P. 2733-2738. DOI: 10.1002/ejoc.201403463.
Kavala V., Naik S., Patel B.K. A new recyclable ditribro-mide reagent for efficient bromination under solvent free condition. J. Org. Chem. 2005. V. 70. N 11. P. 4267-4271. DOI: 10.1021/jo050059u.
Kumar A., Alimenla B., Jamir L., Sinha D., Sinha U.B. Solvent-free methodologies for organic brominations using quaternary ammonium tribromides. Org.Commun. 2012. V. 5. N 2. P. 64-69.
Velusamy P., Pitchumani K., Srinivasan C. Selectivity in bromination of aniline and N-substituted anilines encapsu-lated in β-cyclodextrin. Tetrahedron. 1996. V. 52. N 10. P. 3487-3496. DOI: 10.1016/0040-4020(96)00027-0.
Toda F., Schemeyers J. Selective solid-state brominations of anilines and phenols. Green Chem. 2003. N 6. P. 701-703. DOI: 10.1039/B306612F.
Calo V., Ciminale F., Lopez L., Todesco P.E. A selective bromina-tion of aromatic amine. J. Chem. Soc. Ser. С. 1971. P. 3652-3653. DOI: 10.1039/J39710003652.
Gupta N., Kad G.L., Singh V., Singh J. Regioselective photochemi-cal and microwave mediated monobromination of aromatic com-pounds using 2,4,4,6-tetrabromo-2,5- cyclohexadienone. Synth. Commun. 2007. V. 37. N 19. P. 3421-3428. DOI: 10.1080/00397910701519119.
Khazaei A., Manesh A.A., Safi V.R. Regioselective synthesis of para-bromo aromatic compounds. J. Chin. Chem. Soc. 2005. V. 52. N 3. P. 559-562. DOI: 10.1002/jccs.200500082.
Gorelik M.V., Lomzakova V.İ., Khamidova E.A., Shteiman V.Ya., Kuznetsova M.G., Andrievsky A.M. Regioselective bromination of anilines in the presence of nitrosonium hydrogensulfate in concentrated sulfuric acid. Mendeleev Commun. 1995. V. 5. N 2. P. 65-66. DOI: 10.1070/MC1995v005n02ABEH000460.
Xin-teng D., Guo-bin L. Bromination of anilines by benzyltri-phenyl-phosphonium tribromide. Synth. Commun. 1989. V. 19. N 7-8. P. 1261-1265. DOI: 10.1080/00397918908054532.
Hajipour A.R., Imanieh H., Pourmausavi S.A. 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane tribromide as a highly reactive brominationg agent for aniline derivatives. Synth. Com-mun. 2004. V. 34. N 24. P. 4597-4604. DOI: 10.1081/SCC-200043274.
Borikar S.P., Daniel T., Paul V. An efficient, rapid, and regioselec-tive bromination of anilines and phenols with 1-butyl-3-methylpyridinium tribromide as a new reagent/solvent under mild conditions. Tetrahed. Lett. 2009. V. 50. N 9. P. 1007-1009. DOI: 10.1016/j.tetlet.2008.12.053.
Saikia I., Chaqkraborty P., Sarma M.J., Goswami M., Phukan P. Rapid and total bromination of aromatic compounds using TsNBr2 without any catalyst. Synth. Commun. 2015. V. 45. N 2. P. 211-217. DOI: 10.1080/00397911.2014.956367.
Kumar L., Mahajan T., Sharma V., Agarwal D.D. Envi-ronmentally- benign and rapid bromination of industrially-important aromatics using an aqueous CaBr2-Br2 system as an instant and renewable. Indust. Eng. Chem. Res. 2011. V. 50. N 2. P. 705-712. DOI: 10.1021/ie101498p.
Kumar L., Mahajan T., Agarwal D.D. Chemİnform ab-stract: an instant and facile bromination of industrially im-portant aromatic compounds in water using recyclable CaBr2-Br2 system. Green Chem. 2011. V. 13. P. 2187-2196. DOI: 10.1039/C1GC15359E.
Park M.Y., Yang S.G., Jadhav V., Kim Y.H. Practical and regioselective brominations of aromatic compounds using tetrabutylammonium peroxydisulfate. Tetrahed. Lett. 2004. V. 45. N 25. P. 4887-4890. DOI: 10.1016/j.tetlet.2004.04.112.
Cerichelli G., Luchetti L., Mancini G. Surfactant control of the ortho/para ratio in the bromination of anilines. Tet-rahed. Lett. 1989. V. 30. N 45. P. 6209-6210. DOI: 10.1016/S0040-4039(01)93344-1.
Cerichelli G., Mancini G., Luchetti L. Surfactant control of the ortho/para ratio in the bromination of anilines 2. Tetrahedron. 1994. V. 50. N 12. P. 3797-3802. DOI: 10.1016/S0040-4020(01)90399-0.
Cerichelli G., Luchetti L., Mancini G. Surfactant control of the orthopara ratio in the bromination of anilines. 3. Tetrahedron. 1996. V. 52. N 7. P. 2465-2470. DOI: 10.1016/0040-4020(95)01067-X.
Cerichelli G., Luchetti L., Mancini G. Surfactant control of the ortho/para ratio in the bromination of anilines. 4. Coll. Surf. A: Phys.-Chem. Eng. Asp. 2006. V. 289. N 1-3. P. 226-228. DOI: 10.1016/j.colsurfa.2006.04.039.
Kajgaeshi S., Kakinami T., İnoue K., Kondo M., Naka-mura H., Fujikawa M., Okamoto T. Halogenation using quaternary polyhalides. VI. Bromination of aromatic amines by use of benzyltrimethylammonium tribromide. Bull. Chem. Soc. Jap. 1988. V. 61. N 2. P. 597-599. DOI: 10.1246/bcsj.61.597.
Hosseinzadeh R., Tajbakhsh M., Mohadjerani M., Lasemi Z. Efficient and regioselective bromination of ar-omatic compounds with ethylenebis(N-methylimidazolium) ditribromide (EBMIDTB). Synth. Commun. 2010. V. 40. N 6. P. 868-876. DOI: 10.1080/00397910903019975.
Guo M.J., Varady L., Fokas D., Baldino C., Yu L. A novel tuna-ble aromatic bromination method using alkyl bromides and sodium hydride in DMSO. Tetrahed. Lett. 2006. V. 47. N 23. P. 3889-3892. DOI: 10.1016/j.tetlet.2006.03.191.
Pandule S.S., Shisodia S.U., Patil M.R., Chabukswar V.V. An efficient and regioselective bromination of aro-matic amines and phenols using lanthanum(III) nitrate hexahydrate as a catalyst. Eur. Chem. Bull. 2015. V. 4. N 8. P. 364-367. DOI: 10.17628/ecb.2015.4.364-367.
Firouzabadi H., Iranpoor N., Amani K. Heteropoly acid cesium salt/cetyltrimethylammonium bromide a catalytic heterogeneous sys-tem which highly controls regioselective bromination of aromatic compounds with bromine. J. Mol. Catal. A: Chem. 2003. V. 195. N 1-2. P. 289-294. DOI: 10.1016/S1381-1169(02)00589-7.
Firouzabadi H., Iranpoor N., Kazemi S., Ghaderi A., Garzan A. Highly efficient halogenation of organic com-pounds with halides catalyzed by cerium(III) chloride hep-tahydrate using hydrogen peroxide as the terminal oxidant in water. Adv. Synth. Catal. 2009. V. 351. N 11-12. P. 1925-1932. DOI: 10.1002/adsc.200900124.
Chourdary B.M., Sudha Y., Reddy P.N. Regioselective oxybromination of activated aromatic compounds cata-lysed by ammonium molybdate. Syn. Lett. 1994. N 6. P. 450. DOI: 10.1055/s-1994-22886.
Nath J., Chaudhuri M.K. Boric acid catalyzed bromina-tion of a variety of organic substrates: an eco-friendly and practical protocol. Green Chem. Lett. Rev. 2008. V. 1. N 4. P. 223-230. DOI: 10.1080/17518250902758887.
Gervat S., Leonel E., Barraud J.-Y., Ratovelomanana V. High regioselectivity of bromination of anilines by tetraethylammonium chloride/methanol system as cocatalysts under mild conditions. Tet-rahed. Lett. 1993. V. 34. N 13. P. 2115-2118. DOI: 10.1016/S0040-4039(00)60359-3.
Hanson J.R., Harpel S., Rodriguez Medina İ.C., Rose D. Oxidative bromination of aromatic amides using sodium perborate as oxidant. J. Chem. Res., Synop. 1997. N 11. P. 432-433. DOI: 10.1039/A703217J.
Sharma S.K. Eco-friendly and fast bromination of industrially - important aromatic compounds in water using recyclable AlBr3 - Br2 system. Chem. Internat. 2015. V. 1. N 1. P. 60-70.
Pourmousavi S.A., Salehi P. Synthesis of benzyl triethyl ammonium tribromide and its application as a highly effi-cient and regioselective reagent for the bromination of ac-tivated aromatic compounds. Acta Chim. Slov. 2009. V. 56. N 3. P. 734-739.
Li Z., Sun X., Wang L., Li Y., Ma Y. Silica-supported quinolinium tribromide: a recoverable solid brominating reagent for regioselective monobromination of aromatic amines. J. Brazil. Chem. Soc. 2010. V. 21. N 3. P. 496-501. DOI: 10.1590/S0103-50532010000300015.
Heravi M.M., Abdolhosseini N., Oskooie H.A. Regioselective and high-yielding bromination of aromatic compounds using hexa-methylenetetramine-bromine. Tetrahed. Lett. 2005. V. 46. N 51. P. 8959−8963. DOI: 10.1016/j.tetlet.2005.10.041.
