Basketen

Basketen (IUPAC nomi: pentacyclo[4.4.0.0 ^2,5.0 ^3,8.0 ^4,7 ]dec-9-ene^[1]) C ₁₀ H ₁₀ formulali organik birikma. Bu politsiklik alken va savat bilan tuzilmaviy o'xshashligi uchun nomini olgan basketanning dehidrogenlangan versiyasidir. Uglevodorod tarkibi va noyob tuzilishi tufayli kimyoviy birikma ushbu (CH)₁₀ katak molekulalarining energiya yuzalarini va ularning minimal qiymatlariga qanday omillar ta'sir qilishini o'rganuvchilar uchun katta qiziqish uyg'otadi.^[2] Bundan tashqari, ushbu birikmaning murakkab tuzilishi yuqori kuchlanishli halqa tizimlari kimyosini o'rganayotgan tadqiqotchilarni qiziqtirdi.^[3] Basketen va uning hosilalari oilasi ham muhim kimyoviy va fizik xususiyatlarga ega. Bu molekulalarning barchasi yuqori zichlik bilan birgalikda yuqori standart shakllanish entalpiyasiga ega bo'lib, portlovchi moddalarda mumkin bo'lgan foydalanishga olib keladi.^[4]

Sintez

Basketen siklooktatetraenning izomerlanishi, so'ngra malein angidrid bilan Diels-Alder reaktsiyasi natijasida sintez qilingan. [2 + 2] siklik yuklanish qafas strukturasini yopadi, u sovunlanish va dekarboksillanish orqali basketenga aylanadi.^[5] Sintezni yanada chuqurroq tushuntirish uchun biz sotuvda mavjud bo'lgan siklooktatetraen (1) dan boshlaymiz, bu yerda u termal elektrotsiklik halqani yopishdan o'tadi 2. Keyin 2 dan, 2 va malein angidrid (3) o'rtasida Diels-Alder reaktsiyasi trisilklik struktura 4. Fotokimyoviy sharoitda keyingi [2+2] tsiklik yuklanish 5 ga olib keladi. 5 va natriy karbonat bilan sovunlanishdan keyin 6 ni beradi. Nihoyat, qo'rg'oshin (IV) asetat bilan oksidlovchi dekarboksillanish natijasida yakuniy mahsulot Basketen (7) hosil bo'ladi.

Reaksiyalar

(CH) _n uglevodorodlar oilalari ularning a'zolari boshdan kechirishi mumkin bo'lgan bir-biriga ko'p marta qayta tashkil etilishi bilan tavsiflanadi. Ushbu o'zgartirishlar termal, fotokimyoviy yoki metall kataliz sharoitida boshlanishi mumkin.^[6] Basketen va boshqa qafas molekulalari bog'lanish va reaktivlikning yangi tushunchalarini kashf qilish va sinab ko'rish uchun muhimdir.^[4] Turli reagentlar va reaktsiya sharoitlari bilan o'tkazilgan sinovlar tadqiqotchilarga ushbu murakkab halqa tizimlarining kimyosini va bu (CH)₁₀ tizimlarining qanday qayta tashkil etilishini tushunishga imkon berdi.^[7]

Basketen yordamida bu reaksiyada Nenitskuning uglevodorodini olish mumkin. Basktendan boshlab, reaktsiya teskari Diels-Alder oraliq mahsuloti orqali 110 ˚C da 8 ni berish uchun davom etadi. 8 dan boshlab Nenitzesku uglevodorodini (9) berish uchun 3,3 siljish sodir bo'ladi.^[2]

Basketen, shuningdek, quyidagi termal va fotokimyoviy qayta tartibga solish reaktsiyalariga ham duch kelishi mumkin. Basketen, trisiklo[4.4.0 bilan boshlab. ^02,5 ]deka-3,7,9-trien (8) uni malein angidrid bilan 1:1 qo'shimcha sifatida tutib olindi. Keyin 8 ning konrotary ochilishini keltirib chiqaradigan foto sis, sis, trans-siklooktatrienni beradi (10). Bundan tashqari, 10 -sonli fotosuratlar hosilasini (11) beradi. Yuqorida ko'rsatilganidek, 11 12 ga to'g'ridan-to'g'ri fotokimyoviy (2 + 2) siklizatsiya yopilishidan o'tadi.

Basktene, shuningdek, kumush nitrat bilan eritmada Snoutenega aylanadi

Manbalar

↑ Verevkin, Sergei P.; Martin Kümmerlin; Ernst Hickl; Hans-Dieter Beckhaus; Christoph Rüchardt; Sergei I. Kozhushkov; Rainer Haag; Roland Boese; Jordi Benet-Bucholz (2002). „Thermochemical and X-ray Crystallographic Investigations of Some (CH)₁₀ Hydrocarbons: Basketene, Nenitzescu's Hydrocarbon, and Snoutene“. European Journal of Organic Chemistry. 2002-jild, № 14. Wiley VCH. 2280–7-bet. doi:10.1002/1099-0690(200207)2002:14<2280::AID-EJOC2280>3.0.CO;2-R. 2013-01-05da asl nusxadan arxivlandi. Qaraldi: 2009-11-23. (Archive.is saytida 2013-01-05 sanasida arxivlangan)
↑ ^2,0 ^2,1 Allred, Evan L.; Beck, Boyd R. (1973). „Concurrent thermolysis and photolysis of basketene. Formation and the interrelation of some new (CH)10 isomers“. Journal of the American Chemical Society. 95-jild, № 7. doi:10.1021/ja00788a065.
↑ Gassman, Paul G.; Yamaguchi, Ryohei (1978). „1,8-Bishomocubane“. Journal of Organic Chemistry. 43-jild, № 24. doi:10.1021/jo00418a028.
↑ ^4,0 ^4,1 Aydinli, Betül; Çelik, Murat; M. Serdar, Gültekin; Uzun, Orhan; Balci, Metin (2003). „Controlled Synthesis of Substituted Benzobasketene Derivatives“. Helvetica Chimica Acta. 86-jild.
↑ Smit, W. A.. Organic Synthesis: The Science Behind the Art. The Royal Society of Chemistry, 1998 — 184-bet.
↑ Gajewski, J.J.. Hydrocarbon Thermal Isomerizations. New York: Academic Press, 1981.
↑ Verevkin, Sergei P.; Kümmerlin, Martin; Hickl, Ernst; Beckhaus, Hans-Dieter; Rüchardt, Christoph; Kozhushkov, Sergei I.; Haag, Rainer; Boese, Roland; Bucholz, Jordi-Benet (2002). „Thermochemical and X-ray Crystallographic Investigations of Some (CH)10 Hydrocarbons: Basketene, Nenitzescu's Hydrocarbon, and Snoutene“. European Journal of Organic Chemistry. 2002-jild, № 14. doi:10.1002/1099-0690.

[thermo-1] Verevkin, Sergei P.; Martin Kümmerlin; Ernst Hickl; Hans-Dieter Beckhaus; Christoph Rüchardt; Sergei I. Kozhushkov; Rainer Haag; Roland Boese; Jordi Benet-Bucholz (2002). „Thermochemical and X-ray Crystallographic Investigations of Some (CH)₁₀ Hydrocarbons: Basketene, Nenitzescu's Hydrocarbon, and Snoutene“. European Journal of Organic Chemistry. 2002-jild, № 14. Wiley VCH. 2280–7-bet. doi:10.1002/1099-0690(200207)2002:14<2280::AID-EJOC2280>3.0.CO;2-R. 2013-01-05da asl nusxadan arxivlandi. Qaraldi: 2009-11-23. (Archive.is saytida 2013-01-05 sanasida arxivlangan)

[Allred_and_Evan-2] 2,0 ^2,1 Allred, Evan L.; Beck, Boyd R. (1973). „Concurrent thermolysis and photolysis of basketene. Formation and the interrelation of some new (CH)10 isomers“. Journal of the American Chemical Society. 95-jild, № 7. doi:10.1021/ja00788a065.

[3] Gassman, Paul G.; Yamaguchi, Ryohei (1978). „1,8-Bishomocubane“. Journal of Organic Chemistry. 43-jild, № 24. doi:10.1021/jo00418a028.

[HCA-4] 4,0 ^4,1 Aydinli, Betül; Çelik, Murat; M. Serdar, Gültekin; Uzun, Orhan; Balci, Metin (2003). „Controlled Synthesis of Substituted Benzobasketene Derivatives“. Helvetica Chimica Acta. 86-jild.

[5] Smit, W. A.. Organic Synthesis: The Science Behind the Art. The Royal Society of Chemistry, 1998 — 184-bet.

[Number_7-6] Gajewski, J.J.. Hydrocarbon Thermal Isomerizations. New York: Academic Press, 1981.

[EuroJOC-7] Verevkin, Sergei P.; Kümmerlin, Martin; Hickl, Ernst; Beckhaus, Hans-Dieter; Rüchardt, Christoph; Kozhushkov, Sergei I.; Haag, Rainer; Boese, Roland; Bucholz, Jordi-Benet (2002). „Thermochemical and X-ray Crystallographic Investigations of Some (CH)10 Hydrocarbons: Basketene, Nenitzescu's Hydrocarbon, and Snoutene“. European Journal of Organic Chemistry. 2002-jild, № 14. doi:10.1002/1099-0690.

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