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7Cu(II), Cd(II), Co(II) tuzlarining 2-aminobenzoksazol bilan koordinasion birikmalari sintezi va tadqiqoti
S.R.Razzoqova razzokova89@mail.ru Sh.A.Kadirova S.R.Saddullayeva A.A.Toshov O'zbekiston milliy universiteti
Annotatsiya: Ilmiy adabiyotlarning tahlil natijalariga ko'ra metallarning 2-aminobenzoksazol bilan hosil qilgan komplesklari va ularning xossalari haqida ma'lumot kam keltirilgan. Cu(II), Cd(II) va Co(II) atsetatlarining 2-aminobenzoksazol bilan metall kompleks birikmalarini sintez usullari ishlab chiqildi va shu usullar yordamida metallik kompleks birikmalar sintez qilindi. Sintez qilingan kompleks birikmalarning tarkibi, tuzilishi zamonaviy fizik-kimyoviy usullar; element analizi, IQ-spektroskopiyasi analizlari yordamida tahlil qilindi. Ligand 2-aminobenzoksazol kompleks hosil bo'lish reaksiyalarida benzoksazol halqasidagi azot atomi orqali koordinatsiyaga uchrashi aniqlandi.
Kalit so'zlar: aminobenzoksazol, elektrodonor atom, ligand, infraqizil-spektroskopiyasi, monodentant, element analiz, kvant-kimyoviy hisoblash
Synthesis and research of coordination compounds of Cu(II), Cd(II), Co(II) salts with 2-aminobenzoxazole
S.R.Razzoqova razzokova89@mail.ru Sh.A.Kadirova S.R.Saddullayeva A.A.Toshov National University of Uzbekistan
Abstract: According to the results of the analysis of the scientific literature, there is little information about the complexes formed by metals with 2-aminobenzoxazole and their properties. Methods of synthesis of metal complex compounds of Cu(II), Cd(II) and Co(II) of acetates with 2-aminobenzoxazole were developed and metallic complex compounds were synthesized using these methods. Composition, structure of synthesized complex compounds modern physico-chemical
methods; was analyzed using elemental analysis, IR-spectroscopy analysis. It was found that the ligand 2-aminobenzoxazole is coordinated through the nitrogen atom in the benzoxazole ring during complex formation reactions.
Keywords: aminobenzoxazole, electron donor atom, ligand, infrared spectroscopy, monodentant, elemental analysis, quantum chemical calculation
Kirish. Ma'lumki, biologik faol bo'lgan organik birikmalar tarkibida biometallarni kiritilishi ularni nafaqat zararli tomonlarini kamaytiribgina qolmasdan balki, ko'pgina hollarda biologik faolligini oshiradi yoki yangi biologik xususiyatlarni namoyon qiladi. Shuning uchun yangi, yuqori effektli biopreparatlarni sintezlash va ularni zamonaviy usullar yordamida o'rganish hozirgi kunda dolzarb hisoblanadi.
Hozirgi kunda biologik faol bo'lgan, tuzilishi va xossalari jihatidan katta farq qiladigan, o'zida elektrodonor atomlar tutgan hamda koordinatsion birikmalar hosil qilishga moyil bo'lgan ko'plab organik va noorganik ligandlar mavjud bo'lib, ularning eng muhim sinflaridan biri benzoksazol va uning hosilalari hisoblanadi[1].
Benzoksazol asosidagi fiziologik faol birikmalar molekulasida elektrofil va elektrofob reaksion markazlar bilan kuchli qutblangan guruhlar hosil bo'ladi va bu bilan ular biologik faollikni namoyon etib, fermentlar yoki boshqa hujayralarni o'rab olish uchun dastlabki reagent vazifasini o'taydi. Bu esa, ma'lum tuzilish va xususiyatli koordinasion birikmalarni maqsadli sintez qilishga imkon beradi [2].
2-Aminobenzoksazol (1-rasm), IUPAC nomi 1,3-benzoksazol-2-amin, yalpi formulasi C7H6N2O suvda va boshqa qutbli erituvchilarda eriydigan rangsiz qattiq moddadir. Molyar massasi 134 g/mol, erish temreraturasi 129OC. Ko'pgina murakkab molekulalarni sintez qilishda muhim oraliq mahsulot bo'lib, farmatsevtika, bo'yoq va boshqa birikmalar ishlab chiqarishda qo'llaniladi.
1-rasm. 2-aminobenzoksazol 2-aminobenzoksazollar va ularning o'rnini bosuvchi analoglari turli kasalliklar uchun potentsial dori nomzodlari sifatida tavsiflangan: irritabiy ichak sindromi [3], Altsgeymer kasalligi [4], uyqusizlik [5], surunkali obstruktiv o'pka kasalligi kabi kognitiv disfunktsiyani davolash uchun. ( RDE ingibitori 4) [6], geratit C [7], OIV va yallig'lanish kasalliklaridan [8].
2-aminobenzoksazollar proteazlar, ximaza , butirilxolinesteraza , toroizomeraz II va boshqalarning ingibitorlari sifatida tavsiflangan [9-10], materiallar kimyosida
qo'llaniladi [11] va shuningdek, rozitron emissiya tomografiyasi uchun zondlar sifatida xizmat qiladi [12].
2-aminobenzoksazol bo'yicha ko'plab kelajakdagi tadqiqot yo'nalishlari mavjud. Bularga uning biokimyoviy va fiziologik ta'sirini yanada o'rganish, yangi sintez usullarini ishlab chiqish va dori vositalarini kashf qilish va ishlab chiqish uchun potentsial qo'llanilishini tekshirish kiradi. Bundan tashqari, uning organik sintezda katalizator sifatida, koordinatsion kimyoda ligand sifatida va geterotsiklik birikmalar sintezida qurilish bloki sifatida qo'llanilishi bo'yicha keyingi tadqiqotlar o'tkazilishi mumkin. Nihoyat, analitik kimyoda biologik marker sifatida potentsial foydalanish bo'yicha keyingi tadqiqotlar o'tkazilishi mumkin.
Asosiy qism. Komplesk birikmani sintez qilish uchun metallarning atsetatli va xloridli tuzlaridan foydalanildi.
Kompleks birikmalarning sintezi. Cu2(L)(CH3COO)4H2O kompleks birikmasini sintez qilish uchun 2 mol 2-aminookzazolni 10ml spirtdagi eritmasiga 1 mol Cu(CH3COO)24H2O tuzining suvdagi eritmasidan tomchilatib qo'shildi. Reaksion aralashma 30 minut suv hammomida aralashtirib turgan holda qizdirildi. So'ngra sovutish uchun qoldirildi.
Hosil bo'lgan pushti rangli cho'kma dastlab ochiq havoda, so'ngra 400C gacha qurutish pechida massasi o'zgarmay qolgunga qadar qurutildi. Mahsulot unumi -90,2%, TsUyUq.= 2100C.
Co2(L)(CH3COO)4H2O va Cd4L2Cl2 kompleks birikmalari ham yuqorida bayon etilgan usul bo'yicha sintez qilib olindi. Och yashil rangli Co2(L)(CH3COO)4H2O kompleks birikmasining reaksiya unumi - 72,9%, Tsuyuq.= 2200C.
To'q yashil rangli Cd2(L)(CH3COO)4H2O kompleks birikmasining reaksiya unumi - 83,8%, Tsuyuq.= 2500C.
1-jadval
Olingan kompleks birikmalarning element analiz natijalari
Birikma Reaksiya TSuyuq. Ranggi Topilgan / hisoblangan, %
unumi % 0C C H O N Me
L 95 129 Oq 68,00 67,90 6,90 6,80 9,10 8,90 16,01 15,90 -
Cu2(L)(CH3COO)4-H2O 90,2 210 Pushti 30,83 3,64 34,26 5,99 25,25
30,8 3,81 34,35 5,95 28,09
Co2(L)(CH3COO)4-H2O 72,9 220 Och 30,19 3,56 33,54 5,87 26,83
yashil 30,18 3,58 33,56 5,86 26,84
Cd2(L)(CH3COO)4H2O 83,8 250 To'q 19,96 1,25 6,65 11,64 45,74
yashil 19,95 1,25 6,66 11,65 45,73
Sintez qilingan kompleks birikmalarning element analizi natijalari o'rganildi: Element analizi natijalaridan Me:L=2:1 nisbatda ekanligini ko'rish mumkin.
2-aminobenzoksazolning IQ-Fure spektrlari 4 cm-1 tasvirli DTGS detektor bilan jihozlangan Nicolet iS10 IQ-Fure spektrometri yordamida xona haroratida KBr tabletkalari ko'rinishida yozib olindi. Asosiy holatda 2-aminobenzoksazol
molekulyar strukturaci 6-311G (d,r) bazac to'plamiga ega B3LYR dasturining Gaussian 09 platformasida optimallashtirildi, bu o'z navbatida Li-Yang-Parr korrelyatsion funksionaliga ega uch parametrli almashinuvchan Bekes funksionali gibridi hisoblanadi. 2-aminobenzoksazolning tebranuvchi chastotalari B3LYR darajasida hisoblandi. (RED) Potensial energiyani taqsimlanishini VEDA 4 (Vibrational Energy Distribution Analysis) (Tebranuvchi energiyani taqsimlanish analizi) dasturi yordamida hisoblandi. Masshtabli koeffitsientlarni hisoblash usuli Skot hamda Radom tomonidan tavsiya etilgan usul bilan bir xil.
3-rasm. 2-aminobenzoksazolning metallar bilan hosil qilgan kompleksi
2-rasm. 2-aminobenzoksazolning molekulyar strukturasi va atomlarining raqamlanishi.
Ushbu usul yordamida tautomer formalar geometriyasi optimallashtirildi va umumiy energiyalar (Et), chegaraviy molekulyar orbitallar (MO) energiyasi va chegaraviy MO (AE) o'rtasidagi energetik farqlar hisoblandi. Shuningdek, atomlardagi umumiy zaryadlar taqsimoti hamda yuqori band MO (YUBMO) zaryadning taqsimlanishi hisoblandi.
4-rasm. 2-aminobenzoksazol molekulasining effektiv zaryaadlarining taqsimoti, YUBMO va QBMO orbitallarining qoplanishi.
2-aminobenzoksazolning ikki oyoqli burchagi planar strukturaga nisbatan yaqin yoki silliq ekanligini namoyon qildi. Nazariy natijalarda farazlarimizdagi chastotalarning mavjud emasligi optimallashtirilgan 2-aminobenzoksazol geometriyasi stabil ekanligini ko'rsatdi.
Kvant-kimyoviy hisoblashlar shuni ko'rsatdiki, 2-aminobenzoksazol molekulasidagi azot atomi koordinatsiyada ishtirok etadi, o'z navbatida bu atomlarning koordinatsiyaga uchrashi komplekslarning IQ-spektrida v(M-N) va v(M-O) bog'larining valent tebranishlari 428-499, 546-554, 618-620 sm-1 chastotalarda namoyon bo'lishi bilan tasdiqlandi.
Wavenumber cm-1
5-rasm. 2-aminobenzoksazolning IQ-spektri
:soc :ccc 2500 ¿ccc ieoo iocc eoc
Wa sïnumber cnn-1
6-rasm. Cu2(L)(CH3COO)4H2O tarkibli kompleksning IQ-spektri Mis atsetatli kompleks birikmaning IQ spektrida (IQ fure-spektrometr. Bruker Invenio S-2021) interval 4000-400 sm-1. ATR.) 3374-3309 sm-1 sohada -N-H bog'ining valent tebranishlaridan hosil bo'lgan yutilish maksimumlarini (yoki yutilish chiziqlarini) kuzatish mumkin. 3206-3140 sm-1 sohada kompleks birikma tarkibidagi sp2 gibridlangan =C-H bog'larining valent tebranishi, 3002-2909 sm-1 sohada kompleks birikma tarkibidagi sp3 gibridlangan -S-H bog'larining valent tebranishi, 1664-1601 sm-1 kompleks birikma tarkibidagi C-N, va C=N bog'larining
valent tebranishi, 1425-1366 sm-1 sohada =C-H va -C-H bog'larining deformatsion tebranishlari, 1184-1006 sm-1 sohada -C-O-C- bog'larining valent tebranishlari, 722625 sm-1 (C6H6) -C-H bog'larining deformatsion tebranishlari, 557-457 sm-1 sohada esa Cu-O bog'ining valent tebranishlari hisobiga yuzaga kelgan yutilish maksimumlarini kuzatishimiz mumkin.
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Kadmiy atsetatli kompleks birikmaning IQ spektrida (IQ fure-spektrometr. Bruker Invenio S-2021) interval 4000-400 sm-1. ATR.) 3420-3300 sm-1 sohada -N-H bog'ining valent tebranishlaridan hosil bo'lgan yutilish maksimumlarini (yoki
Wavenumber cm-1
7-rasm. Co2(L)(CH3COO)4H2O tarkibli kompleksning IQ-spektri
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yutilish chiziqlarini) kuzatish mumkin. 3217-3046 sm-1 sohada kompleks birikma tarkibidagi sp2 gibridlangan =C-H bog'larining valent tebranishi, 1691-1592 kompleks birikma tarkibidagi C-N, va C=N bog'larining valent tebranishi, 1464 sm-1 sohada =C-H va -C-H bog'larining deformatsion tebranishlari, 1271-1064 sm-1 sohada -C-O-C- bog'larining valent tebranishlari, 741-604 sm-1 (C6H6) -C-H bog'larining deformatsion tebranishlari, 460 sm-1 sohada esa Cd-O bog'ining valent tebranishlari hisobiga yuzaga kelgan yutilish maksimumlarini kuzatishimiz mumkin.
Xulosa qilib aytadigan bo'lsak sintez qilingan kompleks birikmalarning tarkibi, tuzilishi va xossalari IQ-spektroskopiyasi, SEM-EDX usuli, termik analiz va DQEC kabi fizik-kimyoviy usullar yordamida o'rganildi. Co(II), Ni(II), Cu(II) va Zn ligand 2-aminobenzoksazol molekulacidagi azot atomi orqali koordinasiyaga uchrashi ko'rsatildi. Bundan tashqari, termik analiz natijalariga ko'ra, kompleks birikmalar tarkibida suv molekulalari mavjud ekanligi, shuningdek komplekslarning parchalanishi 200-800OC harorat intervalida sodir bo'lishi aniqlandi, bu o'z navbatida yuqoridagi eksperimental tavsifimizni yana bir bor tasdiqladi. Benzoksazolning yangi hosilasi 2-aminobenzoksazol molekulasining reaksion qobiliyatini va kompleks hosil qilish xususiyatlarini o'rganish maqsadida ayrim 3d-metallarning tuzlari olinib, ular bilan bir necha sintez ishlari olib borildi. Sintez qilingan kompleks birikmalarning tarkibi, tuzilishi va xossalari zamonaviy fizik-kimyoviy tadqiqotlar bilan o'rganilganda kompleks birikmalar tarkibida metall va atsidoligandlar tabiatining ta'siri kuzatildi.
Foydalanilgan adabiyotlar
1. Sharma J., Mishra P., Bhadoria J. 2-aminophenol as a leading reactant for the one pot synthetic strategies towards benzoxazole derivatives // Results in Chemistry. -2022. -V. 4. ISSN 2211-7156 10.1016/j.rechem.2022.100670.
2. Arulmurugan S., Kavitha H. P., Vennila J. P. Review on the Synthetic Methods of Biologically Potent Benzoxazole Derivatives //Mini-Reviews in Organic Chemistry. - 2021. - V. 18. - I. 6. - P. 769-785.
3. Osmaniye D. et al. Synthesis of some new benzoxazole derivatives and investigation of their anticancer activities //European Journal of Medicinal Chemistry. - 2021. - V. 210. - P. 112979. doi.org/10.1016/j.ejmech.2020.112979
4. Muhammed M. T. et al. Synthesis, antimicrobial activity, and molecular modeling studies of some benzoxazole derivatives //Letters in Drug Design & Discovery. - 2022. - V. 19. - I. 8. - P. 757-768. 10.2174/1570180819666220408133643
5. Liu K. G. et al. Identification of a series of benzoxazoles as potent 5-HT6 ligands //Bioorganic & Medicinal Chemistry Letters. - 2009. - V. 19. - I. 4. - P. 1115-1117. 10.1016/j.bmcl.2008.12.107
6. Chen S. C. et al. Mild direct amination of benzoxazoles using interpenetrating Cobalt (II)-based metal-organic framework as an efficient heterogeneous catalyst //Molecular Catalysis. - 2018. - V. 450. - P. 104-111.10.1016/j.mcat.2018.03.011
7. Cox C. D. et al. Discovery of the dual orexin receptor antagonist [(7 R)-4-(5-chloro-1, 3-benzoxazol-2-yl)-7-methyl-1, 4-diazepan-1-yl][5-methyl-2-(2 H-1, 2, 3-triazol-2-yl) phenyl] methanone (MK-4305) for the treatment of insomnia //Journal of medicinal chemistry. - 2010. - V. 53. - I. 14. - P. 5320-5332. 10.1021/jm100541c
8. Frutos R. P. et al. Development of a Practical Process for the Synthesis of PDE4 Inhibitors //Organic Process Research & Development. - 2016. - V. 20. - I. 5. - P. 982-988. 10.1021/acs.oprd.6b00104
9. Neyts J. et al. Structure- activity relationship of new anti-Hepatitis C virus agents: Heterobicycle- coumarin conjugates //Journal of medicinal chemistry. -2009. - V. 52. - I. 5. - P. 1486-1490. 10.1021/jm801240d
10. Odame F. et al. A new synthetic method for tetraazatricyclic derivatives and evaluation of their biological properties //ChemistrySelect. - 2018. - V. 3. - I. 48. -P. 13613-13618. 10.1002/slct.201802930
11. Slachtova V., Chasak J., Brulikova L. Synthesis of Various 2-Aminobenzoxazoles: The Study of Cyclization and Smiles Rearrangement //ACS omega. - 2019. - V. 4. - I. 21. - P. 19314-19323. 10.1021/acsomega.9b02702
12. Potashman M. H. et al. Design, synthesis, and evaluation of orally active benzimidazoles and benzoxazoles as vascular endothelial growth factor-2 receptor tyrosine kinase inhibitors //Journal of medicinal chemistry. - 2007. - V. 50. - I. 18. -P. 4351-4373. 10.1021/jm070034i
13. Z. Yakhshieva, R. Kalonov, D. Kaigorodov, E. Kalinin, S. Chepur, E. Ivchenko, O. Mustaev. Problems of the Biomedical Technologies Development and Directions for their Solution // Journal of Biomimetics, Biomaterials and Biomedical Engineering Submitted: 2021-05-10 ISSN: 2296-9845, Vol. 53, pp 1-9 Accepted: 2021-05-11 © 2021 Trans Tech Publications Ltd, Switzerland.
14. Yakhshieva Z.Z., U.T. Ahmadjonova, Yo.T.Ahmadjonova. Technogenic Transformations of the Aidar-Arnasay Lake System and their Geological Consequences.//Annals of the Romanian Society for Ceel Biology, (2021) P.2912-2916.
15. Qutlimurotova N., Mahmadoliev S., Smanova Z., Yakhshiyva Z., Tursunkulov Z.Amperometric determination of cerium (III) using 2,7-dinitrozo-1,8-dihydroxynaphthalene-3,6-disulfonic acid solution// PERIODICO TCHE QUIMICA.Vol.17, No 36 2020, pp736-745.
16. Yakhshieva Z, Abdurakhmonov B., Kalonov R. Apoplication Of Oxyazo Compounds In The Definition Of The ion Bi(V)// European Journal of Molecular & Clinical Medicine. №7. P.1058-1066.
