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KiMYA PROBLEMLORi № 1 2014
UOT 547.74
2-FENiL-DORDOVOZLi PiRROLLARIN SADO METODLA SiNTEZi
A.^.Safarova, i.M.Ohmadov, i.O.Oliyev, M.M.Qurbanova, A.M.Maharramov
Baki Dovlat Universiteti, AZ1148 Baki, Z. Xalilov kugasi, 23; e-mail. idrismecid@yahoo. com
Pirrrol halqasi hayat ahamiyyatli bir gox tabii birla^malarin - xlorofil, hemoqlobin, vitamin B12 va alkaloidlarin tarkibina daxildir. Maqala 2-fenil-pirrollarin sada metodla sintezina, yani 2-benzoil-4-brom-etilpenten-4-karboksilat ila aromatik aminlarin reaksiyalarinin oyranilmasina hasr olunmu^dur.
Agar sozldr: xlorofil, hemoqlobin, alkaloid, pirrol
Muasir dovrda pirrol kimyasina maraq xeyli artmaqdadir. Buna sabab pirrol halqasinin hayati zaruriyyat da§iyan bir 9ox onamli tabii birla§malarin — xlorofil, hemoqlobin, vitamin Bi2 va alkaloidlarin tarkibina daxil olmasidir [1]. Pirrol birla§malari asasinda sintez olunan va tarkibinda porfirin, ftalosianin va BDP (bordipirrolometan boyalari) strukturu saxlayan birla§malar elektrik va optiki elektronika sanayesinda tatbiq olunan sensorlarin va fotostabilizatorlarin hazirlanmasinda avaz olunmaz materiallardir [2-4]. Pirrolun 2,5-ditiofen toramalari asasinda elekropolimerla§ma metodu ila sintez olunan yarimke9irici polimerlar zaif elektrik carayanin tasiri ila qirmizi, ya§il va mavi rang verdiyi u9un internet-televiziya texnologiyasinin inki§afinda son daraca onamli rol oynayirlar [5-7].
2006-ci ilda J.V.Huffman va
amakda§lari [8] subut etmi§lar ki, 2-fenil-pirrolun bazi toramalarinin yuksak fizioloji aktivliya sahib olmasinin sababi onlarin qurulu§larinin CB1 va CB2 "cannabimi-metric" reseptorlara ox§ar olmasidir. Bu maqaladan sonra 2-fenil-pirrol kimyasina diqqat 9ox artmi§ va onlarin sada — yuksak 9iximla sintezi pirrol kimyasinin asas problemlarindan biri olmu§dur. 9dabiyyatda malum metodlarla 2-fenil-pirrollarin sintezi 22-40% arasi dayi§ir [9,10].
9vvalki 9ali§malarimizda gostaril-mi§dir ki, 1,3-diketonlarin 2-bromallil toramalarinin enaminlari super asas muhutunda 70-85% 9iximla muxtalif pirrol toramalari amala gatirir [11].
Taqdim olunan maqala 2-fenil-pirrollarin sada metodlarla sintezina, yani 2-benzoil-4-brom-etilpenten-4-karboksilat (1) ila aromatik aminlarin reaksiyalarinin oyranilmasina hasr olunmu§dur:
A.§.S3F3ROVA va b.
103
Ar= C6H5 (5), C6H5-CH2 (6) , СбИзССИэ) CH (7)
Sintez olunan enamin (2-4) va 2-fenil-pirrollarrn (5-7) qurulu§lari ÍQ va H1 , C13 NMR-spektroskopiyasi vasitasila öyranilmi§dir. Nazik aluminium-silikagel
(Maersk) tabaqasi üzarinda analiz göstarir ki, enaminlar iki handasi izomerin qan§igindan ibaratdir va super asasi mühitda har iki izomer pirrol amala gatirir.
TöCRUBi Hisse
Sintez olunan maddalarin NMR-spektrlari Bruker DPX400 cihazinda (CDCl 3) öyranilmi§dir. Maddalarin optiki aktivliyi (dönma bucaqlari) CM-2 avtomatik polyarimetrda öl9ülmü§dür. iQ spektrlari Perkin Elmer 1600 FTiR spektrometrda 93kilmi§dir. Nazik tabaqa üzarinda analiz ÜB i§iq = 254 Tim) vasitasib müayyan edilmi§dir.
2-benzoil-4 brom-etilpenten-4-karbok-siat(1)-in sintezi
5 ml quru THF-da hall olmu§ 960 mq (5mmol) benzoiletilasetat üzarina quru azot mühitinda 120 mq (5.0 mmol) NaH alava edib otaq temperaturunda 2 saat qari§dirdiqdan sonra üzarina 1q (5.0 mmol ) 2,3-dibrompropenin 5ml THF-da mahlulunu damladaraq, qari§dirma 3 saat davam etdirilir.
Reaksiya qari§igim avvalca su, sonra 2-3% HCl mahlulu ila i§ladikdan sonra, efir ila (3x25) ekstraksiya edib, MgSO4 üzarinda qurudulur. Halledicini qovduqdan sonra, madda (1) kolon xromotoqrafiyasi ila (halledici=etilasetat:heksan=1:4) tamizlanir, o özlü sari mayedir R7=0.54, q.t.126-127 (1mm) [12].
2-benzoil-4-brom-etilpenten-4-karboksilat (1) asasinda (2-4) enaminlarin sintezi
(2-4) enaminlar (1L) metodu asasinda sintez olunmu§dur. 0.01 mol (1), 0.015 mol
amin va katalitik miqdar PTSK qari§igmi 20 ml benzol mahlulu Din-Stark aparatinda 10 saat qaynadilir, qari§iq 1 geca otaq temperaturunda saxladiqdan sonra, fla§ kolon xromatoqrafiyasi ila tamizlanir. 2-brom-5-fenilamin-etilpenten-4-karbok-silat (2).
1.89 q (75%) özlü maye. iQ-spektri: 3040, 2920, 1650, 1560, 1280, 1198 sm-1 H1 PMR (400MHZ, CDCl3):1.25 (t,J=7.0 Hz, 3H), 3.45 ( s,2H), 4.20 (q, J=7.0 Hz, 2H), 5.40 (s, 1H), 5.55 (s, 1H ), 7.00-7.61 (m, 10 H), 10.0 (s, NH).
1,2-difenil- 5 -metil -etil -1H - pirrol -3-karboksilat - (6)
2.2 q (82 %) özlü maye, ÍQ - spektr :
3040 -2970, 1540, 1425, 1380 sm^.H1 -PMR ( 400 MHz, CDCI3) : Я , 1.14 (t .7.0 Hz , 3H ), 2.10 (S,3H), 4.12 (q, J = 7.0 Hz, 2H ), 6.55 (s, 1 H ), 7.00 - 7.50 (m , 10 H).
C13- NMR (100 MHz, CDCI3) : S , 12.5, 14.6, 48.4, 60.0, 98.2, 110.2, 125.6, 127.4 ,127.8, 127.9, 129, 130.6, 132.6, 137.8, 138.4, 164.8 .
(R)- 1 - (a- feniletilamin )- 2- fenil - 5 - metil - etil - 1 -H - pirrol - 3-karboksilat (7).
1.9 q (70 %), san qati maye [^]D20 = +184.98 ( с 0.47 , CHC13 ). ÍQ - spektr: 3050 , 2980, 1675, 1535 sm -1. H1 - PMR ( 400
104
2-FENiL-DORDavaZLi PiRROLLARIN
MHz ,CDC13 ) : s , 1.1 (t, J = 7.0 Hz ,3H ), 1.78 (d ,J = 7.1 Hz, 1H), 6.38 (S,1H ), 7.0 (d ,J= 7.5 Hz , 2H ), 7.2 -7.50 (m ,8H ) (§akil 1).
C13-NMR (CDCI3) : &' 14.2, 14.3, 19.1, 53.2, 59.0, 110.8 , 113.0, 126.0, 127.2, 128.0, 128.3, 128,7, 128.8,129.2, 130.2, 130.8, 133.0, 139.2, 142.4, 164.5 (§akil 2).
§akil 1. (R)-1 -(a-feniletilamin)-2-fenil-5-metil-etil-1 -H-pirrol-3-karboksilatin (7) rf-PMR-spektri.
§3kil.2. (R)-1 -(a-feniletilamin)-2-fenil-5-metil-etil-1 -H-pirrol-3-karboksilatin (7) C13 NMR-spektri.
0D0BiYYAT
1. Трофимов Б.А., Михалева А.И., Шмидт Е.Ю., Собенина Л.Н. Химия пиррола. Новые страницы". Новосибирск: Наука. 2012. 383с. //Trofmov B.A., Mikhaleva A.I., Dhmidt E.Yu., Sobenina L.N. Khimiya pirrola. Noviye stranise. Novosibirsk: Nauka. 2012. 383 p.
2. Wada M., ito S., Uno H., Murashima T. Et al. Syntesis and optical properties of a new class of pyromethene - BF2 Complexes fused with rigid bicycle rings and benzo derivatives. // Tetrahedron Letters". 2001. v. 42. p. 6711.
3. Алещенков С.Э., А.В.Чепраков, И.П.Белецкая. Тетраантра [2,3- b,g,l,q] порфирин. //ДАН. 2008. Т. 422. N 2. С.
189 . //Aleshenkov S.E., Cheprakov A.V., Beleskaya I.P. Tetraantra [2,3-b,g,l,q]por-firin . // DAN. 2008. v.422. N2. p. 189.
4. Guliyev R., Ozturk S., Sahin E., Akkaya E.U. Expanded Bodipy Dyes : anion sensing using a Bodipy with an Additional dif-luoroboran bridge. //Organic letters " 2012. v 14. N 6. 1528.
5. Tarkuc S., Sahmetlioglu E., Tanyeli C. Et al. Electrochromic properties of poly (1 -phenyl ) - 2, 5 - di- ( 2- thienyl ) - 1H-pyrrole- co-3, 4- ethylenedioxy thiophene) and its application in electrochromic devices. // Optical Materials. 2008.v. 30. p. 1489.
A.§.S3F3ROVA va b.
105
6. Abashev G.G., Bushueva A.Y., Shklyaeva. N-Substituted 2, 5-(2- thienyl) pyrroles, production, properties, and electrochemical polymerization. //Chem.of.Heterocyclic compounds. 2011. V.47. N2. p.130.
7. Yildiz E., Camurlu P., Akhmedov i., Toppare L. A Soluble Conducting polymer of 4- ( 2,5- di - thiophen -2- yl- 1H- pyrrol-1-yl ) benzenamine and its multichromic copolymer with EDOT //J. of Electroanaltical chemistry. 2008.V.612. N2. p 247.
8. Huffman J.V., Padqett L.V., Martin B.R. 1-Alkyl- 2- aryl-4- (1- naphthoyl) pyrroles: New high affinity liqands far the cannabinoid CB, and CB2 receptors. //Bioorganic and Medicinal Chemistry Letters. 2006. V. 16. P. 5432.
9. Трофимов В.А., Коростова С.Е., Балабанова Л.Н., Михалева А.И. Пирролы из кетоксимов и ацетилена. //Жорх. 1978. Т.14. N. 8. С.1733. //Trofmov V.A., Korostova S.E., Balabanova L.N., Mikhaleva A.I. Pirroli iz
ketoksimov i asetilena //J. Organicheskoy thimii. 1978. V.14. N8. p.1733.
10. Miyaura N., Yanagi T., Suzuki A. The Synthesis of 2- arylpyrroles from 2-bromopyrroles // Synth.Commun. 1981. 11. P.513.
11. Ayhan.S Demir, Idris M.Akhmedov and Ozge Sesenoglu. Synthesis of 1,2,3,5-tetrasubstituted pyrrole derivatives from 2-(2-bromallyl)-1,3-dicarbonyl compounds //Tetrahedron. 2002.v. 58. p. 9793.
12. Ахмедов Ш.Т., Садыхов Н.С., Исмаилов
B.М. и др. Алкилирование Р-дикарбонилъных соединений 1,2,3-тригалоген пропанами как метод синтеза р-замещенных фуранов. //Химия Гетероцикл. Соед. 1986. N 2.
C.1602. // Akhmedov Sh.T., Sadikhov N.S., Ismailov V.M. et al. Alkilirovaniye /З-dikarbonilnikh soyedineniy 1,2,3-trigalogen propanami kak method sinteza /З-zameshennikh furanov. //Khimiya qeterosikl. Soyed. 1986. N2. p.1602.
СИНТЕЗ ЗАМЕЩЕННЫХ 2-ФЕНИЛ ПИРРОЛОВ ПРОСТЫМ МЕТОДОМ
А.Ш.Сафарова, И.М.Ахмедов, И.А.Алиев, М.М.Курбанова, А.М.Магеррамов
Пиррол входит в состав многих жизненно важных природных соединений, таких как хлорофилл, гемоглобин, витамин В12 и физиологически активных алкалоидов. Работа посвящена изучению простого метода синтеза 2-фенил-пирролов - реакции взаимодействия 2-бензоил-4-бром-этилпентен-4-карбоксилата с ароматическими аминами. Ключевые слова: хлорофилл, гемоглобин, алтлоид, пиррол.
SYNTHESIS OF 2-PHENYL-SUBSTITUTED PYRROLES THROUGH SIMPLE METHOD
A.S.Safarova, I.M.Akhmedov, I.A.Aliev, M.M.Kurbanova, A.M.Makharramov
Pyrrole is a part of many vitally important compounds such as chlorophyll, hemoglobin, vitamin B12 and physiologically active alkaloids. The work deals with research into simple method of synthesis 2-phenyl pyrroles - reaction of interaction of 2-benzoil-4-bromine-ethylpenten-4-carbpxilate with aromatic amines.
Keywords: chlorophyll, hemoglobin, alkaloid, pyrrole.
Redaksiyaya daxil olub 21.11.2013.
