Year 2019, Volume 3 , Issue 1, Pages 8 - 20 2019-06-30

Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları
Ullmann Type N-Arylation Reactions of Iodo Pyrazoles with Phenyl Boronic Acid in Cu2O Catalyst

Melek Hinis [1] , Ayfer Mentes [2]


Ullmann tipi reaksiyonlar bakır katalizörü kullanılarak pirazollerin N-arilasyonu gerçekleştirmek için en etkili yöntemlerden birisidir. Geleneksel yöntemlerle gerçekleştirilen Ullmann reaksiyonu yüksek sıcaklıklarda ve stokiyometrik oranda bakır reaktifleri kullanılarak sert reaksiyon koşulları altında gerçekleşmektedir. Daha verimli bakır katalizörlerinin gelişmesi ile bu alanda yapılan çalışmalar devam ederek hafif koşullar altında oldukça verimli bakır/ligant sistemleri geliştirildi. Ullmann tipi reaksiyonların verimliliğini arttırmak için birçok bakır/ligant kombinasyon reaksiyonlarının nispeten yumuşak koşullar altında gerçekleştirdiği bilinmesine rağmen, son yıllarda ligant içermeyen ve "yeşil" çözücülerle ya da çözücüsünden arındırılmış daha basit katalizör sistemleri üzerine çalışmalar yapılmaktadır.

Bu çalışmada pirazollerin ılıman şartlarda N-arilasyonuna katkı sağlaması amacıyla fenil boronik asit ile 4-iyodo-1H-pirazol (I-Pz) veya 4-iyodo-3,5-dimetil-1H-pirazolün (I-DMPz) Cu2O katalizörlüğünde N-arilasyonu ile 4-Iyodo-1-fenil-1H-pirazol (Ph-IPz) ve 4-Iyodo-3,5-dimetil-1-fenil-1H-pirazol (Ph-IDMPz) bileşikleri literatürdeki yönteme göre uyarlanarak sentezlenmiştir. 4-İyodo pirazollerin fenil boronik asit ile N-arilleme reaksiyonları Cu2O katalizörlüğünde, atmosferik koşullarda, oda sıcaklığında ve metil alkol içerisinde herhangi bir baz ve ligant kullanılmadan gerçekleştirilmiştir. Böylece daha ılıman koşullarda Ullmann reaksiyonu ile ilk defa Ph-IPz ve Ph-IDMPz’ın sentezi gerçekleştirilmiştir.

Sentezi gerçekleşen Ph-IPz ve Ph-IDMPz’in yapıları FT-IR, NMR ve GC-MS kütle spektrumları alınarak karakterize edilmiştir. Bileşiklerin NMR ve FT-IR spektrumunda hem pirazole hem de fenil grubuna ait karakteristik pikler gözlenmiştir.Elde edilen Ph-IPz ve Ph-IDMPz bileşiklerinin 1H-NMR spektrumlarında N-H proton piklerinin görülmemesi fenil grubunun pirazole NH’dan bağlandığının bir göstergesidir. 13C-NMR spektrumlarında 4-sübstitüe pirazoller için belirleyici olan  C4 karbon piklerindeki kaymalar da bileşiklerin yapılarını doğrulamaktadır.

Ullmann type reactions are one of the most effective methods to carry out the N-arylation of the pyrazole using copper catalyst. The Ullmann reaction carried out by conventional methods occur under hard reaction conditions using copper reagents at stoichiometric ratio and at high temperatures. With the development of more efficient copper catalysts, studies in this field have been continued and very efficient copper/ligand systems have been developed under mild conditions. Although it is known that many of copper / ligand system reactions are carried out under relatively mild conditions to increase the efficiency of Ullmann type reactions, in recent years, studies have been made on simpler catalyst systems which are  ligand free and "green" solvents or solvent free.

In this study, in order to contribute to N-arylation of pyrazoles in mild conditions, 4-Iodo-1-phenyl -1H-pyrazole (Ph-IPz) and 4-iodo-3,5-dimethyl-1-phenyl-1H-pyrazole (Ph-IDMPz) compounds were synthesized according to the methods adapted from literature with N-arylation reaction of 4-Iodo-1H-pyrazole (4-IP) or 4-iodo-3,5-dimethyl-1H-pyrazole (4-IDMPz) with phenyl boronic acid in the prences of Cu2O catalyst. N-Arylation reactions of 4-iodopyrazols with phenyl boronic acit were carried out the presence of Cu2O catalyst, at atmospheric conditions, at room temperature, in methyl alcohol and without the use of any base and ligand. In this way , the synthesis of Ph-IPz and Ph-IDMPz was carried out for the first time with Ullmann reaction under the milder conditions.

Synthesized ligands Ph-IPz and Ph-IDMPz were characterized by FT-IR, NMR and GC-MS mass spectra. The NMR and FT-IR spectra of the compounds showed characteristic peaks of both the pyrazole and the phenyl group. The absence of N-H proton peaks in the 1 H-NMR spectra of the obtained Ph-IP 2 and Ph-IDMP 2 compounds indicates that the phenyl group is attached from the pyrazole NH. The shifts in the C4 carbon peaks which are determinant for 4-substituted pyrazoles in the 13C-NMR spectra also confirm the structure of the compounds.

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Primary Language tr
Subjects Basic Sciences
Journal Section Research Article
Authors

Orcid: 0000-0002-6618-3992
Author: Melek Hinis (Primary Author)
Institution: AKSARAY ÜNİVERSİTESİ, FEN-EDEBİYAT FAKÜLTESİ
Country: Turkey


Author: Ayfer Mentes
Institution: AKSARAY ÜNİVERSİTESİ, FEN-EDEBİYAT FAKÜLTESİ
Country: Turkey


Dates

Publication Date : June 30, 2019

Bibtex @research article { asujse475842, journal = {Aksaray University Journal of Science and Engineering}, issn = {}, eissn = {2587-1277}, address = {Aksaray Üniversitesi, Fen Bilimleri Enstitüsü, Merkez Kampüs, 68100 Aksaray}, publisher = {Aksaray University}, year = {2019}, volume = {3}, pages = {8 - 20}, doi = {10.29002/asujse.475842}, title = {Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları}, key = {cite}, author = {Hinis, Melek and Mentes, Ayfer} }
APA Hinis, M , Mentes, A . (2019). Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları. Aksaray University Journal of Science and Engineering , 3 (1) , 8-20 . DOI: 10.29002/asujse.475842
MLA Hinis, M , Mentes, A . "Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları". Aksaray University Journal of Science and Engineering 3 (2019 ): 8-20 <http://asujse.aksaray.edu.tr/en/issue/41539/475842>
Chicago Hinis, M , Mentes, A . "Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları". Aksaray University Journal of Science and Engineering 3 (2019 ): 8-20
RIS TY - JOUR T1 - Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları AU - Melek Hinis , Ayfer Mentes Y1 - 2019 PY - 2019 N1 - doi: 10.29002/asujse.475842 DO - 10.29002/asujse.475842 T2 - Aksaray University Journal of Science and Engineering JF - Journal JO - JOR SP - 8 EP - 20 VL - 3 IS - 1 SN - -2587-1277 M3 - doi: 10.29002/asujse.475842 UR - https://doi.org/10.29002/asujse.475842 Y2 - 2019 ER -
EndNote %0 Aksaray University Journal of Science and Engineering Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları %A Melek Hinis , Ayfer Mentes %T Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları %D 2019 %J Aksaray University Journal of Science and Engineering %P -2587-1277 %V 3 %N 1 %R doi: 10.29002/asujse.475842 %U 10.29002/asujse.475842
ISNAD Hinis, Melek , Mentes, Ayfer . "Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları". Aksaray University Journal of Science and Engineering 3 / 1 (June 2019): 8-20 . https://doi.org/10.29002/asujse.475842
AMA Hinis M , Mentes A . Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları. Aksaray J. Sci. Eng.. 2019; 3(1): 8-20.
Vancouver Hinis M , Mentes A . Iyodo Pirazollerin Cu2O Katalizörlüğünde Fenil Boronik Asit ile Ullmann Tipi N-Arilasyon Reaksiyonları. Aksaray University Journal of Science and Engineering. 2019; 3(1): 20-8.