Olefinlerden fatolotik yolla tek aşamalı alfa, beta- doymamış karbonil bileşikleri sentezi
One-pot conversion of olefinsto alfa, beta-unsaturated carbonyl conpounds
- Tez No: 39838
- Danışmanlar: PROF.DR. OLCAY ANAÇ
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1994
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 43
Özet
ÖZET Metil sübstitüe sikloheksenonlar canlıların salgılarında da bulunabilen önemli doğal bileşiklerdir. Kozmetik, parfüm ve ilaç endüstrilerinde kullanılabilirlik özellikleriyle sentezleri önem kazanmıştır ve çoğu sentez reçeteleri patentlerle korunmuştur. Bu derece yararlı çıkış bileşiklerinin sentezlerinde bir çok sorunla karşılaşılmaktadır. Bu sorunlar çok aşa malı reaksiyonlar, düşük verim, pahalı ve güç elde edilen çıkış maddelerinin kullanılması şeklinde özetlenebilir. Çalışmamızın amacı tek aşamalı olan“Metil sübstitüe sikloheksenin singlet oksijen ile fotolitik reaksiyonu ”ile metil sübstitüe sikloheksenonların sentezini incelemektir. Her aşamada ele geçen ürünlerin analizleri Gaz Kromatografisi ve ince Tabaka Kromatografisi ile gerçekleştirilmiş, tanımlanmalar ise IR-Spektroskopisi ve zaman zaman ^-NMR Spektroskopisi ile yapılmıştır. vı
Özet (Çeviri)
There are few compounds that have more potential and versatility in organic synthesis than cyclic and acylic a,/3-conjugated carbonyl compounds. The a,£-unsaturated carbonyls behave as dienophiles in the Diels Alder reaction. They react with guanidine to give pyrimidines, hydroxylamine to give isoxazeles, hydrazine to give pyrazoles and hydrazoic acid to give 1,2, 3-triazoles. The a,J3-unsaturated ketones exhibit a wide variety of addition reactions, some reagents adding to the carbonyl group, others adding to the carbon-carbon double bond, whilst some, e.g. Grignard reagents, may add to the conjugated systems with subsequent rearrangement ; 0 OMqBr II I y RCCH=CHR + R“MgBr> RC=CHCHR'R”0 H70 II -» RCCH2CHR'R“ Halogens and halogen acids add to the double bound in the latter case the halogen atom usually becaming attached to the J3-carbon atom. Another important group of addition reactions comprises the Michael addition of compounds, such as malonic, cyonoacetic and acetoacetic acid esters, easily capable of yielding carbanions in the presence of catalytic quantities of alkali. o o RCH=CHCR' + CH2(COOEt)2 Na0Et > RCHCH2CR' CH(COOEt)2 VllThe a,/3-unsaturated carbonyl compounds useful as perfumes, medicines. Yet the available sources of these valuable materials are generally tedious, multistep synthetic routes or expensive commercial suppliers. The starting compounds for the synthesis of a, J3- conjugated carbonyl compounds are alkenes, cycloalkenes, ketones, diesters. Although several different reaction patways are available for the synthesis of these conjugated carbonyls no approach has been generally applicable to the simple C-5 through C-8 cycloalkenes. In our study 1,5-cyclooctadien, 1-decen, 1-methyl-l- cyclohexen, 4 -methyl -1 -eye lohexen, 3 -methyl -1-cyclohexen, were used as starting compounds for the synthesis of carbonyl compounds by an in situ photooxygenation elimination procedure. Our synthesis is based on the decades-old observations of Schenck and co-workers, which demonstrated that allylic hydroperoxides are handily prepared by reaction of alkenes with photochemically generated singlet oxygen and these materials are easily converted to enones under mild conditions. The cycloalkenes, exemplified by 1 -methyl- 1-cyclohexen as shown in Scheme I, are readily photooxygenated in the presence of acetic anhydride and base to yield directly cycloalkenones after aqueous work up and distillation. O2. AC2O, Pyridine 4-Dimethylaminopyridine CH2C12 '0, V) a CO s X OH ^k^OOH Ac70 + u -. Base OOAc OOAc Scheme I -Photooxygenation of 1-methyl-l-cyclohexen. Vlll02 ^A^yOOH Ac,0 /”^yOOAc ^~yO * u Base »L> +U OÜH CH2=CH(CH2)7CH3 OOAc 02 * CH2CH=CH(CH2)6CH3 0 Ac20 Base CH2CH=CH(CH2)6CH3 z^> H-CCH=CH(CH2)6CH3 f\ 102 |-^yOOH J^yOOH Ac20 J^yOOAc \^ > k^J + k J Base J L J + 1 Jl 0 r^N-OOAc Base > ^N^w Is^J -HOAc :Sen :Sen> 3Sen 2Sen> Sen + 02 {lkg) Singlet oxygen can react with various substrates in three different ways: 1-1,4-Cycloaddition with conjugated dienes, frequently resulting in the generation of endoperoxides (B). 2-1,2-Cycloaddition, a reaction that occurs when olefins and enamines react with 02(lbs) with formation of 1,2- dioxetanes ( C ). 3- An“ene”reaction, with olefins having two or more alkyl substituents, to form allylic hydroperoxides (A). xx~s-- c0 -^ - s: XIX
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