Doymamış karbonil bileşikleri ve türevlerinin diaza bileşikleriyle reaksiyonları
Başlık çevirisi mevcut değil.
- Tez No: 55660
- Danışmanlar: PROF.DR. OLCAY ANAÇ
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Diazo bileşikleri, Karbonil kompleksler, Diazo compounds, Carbonyl complexes
- Yıl: 1996
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
DZET Birden çok sayıda karbonil fonksiyonu içeren siklopropan türevleri organik sentezlerde çok gereksinim duyulan ara bileşiklerdir. Bu bileşiklerden çıkılarak gerçekleştirilecek çeşitli reaksiyonlarla çok sayıda kıymetli doğal bileşik sentetik yaldan elde edilebilir. Bu nedenlerle poli-karbonil sübstitüe siklopropan bileşikleri“Elektrof ilik siklopropanlar”ilaç, zararlı yok edici, kozmetik ve polimer endüstrilerinde kullanım olasılığına sahiptirler. Diazo bileşiklerinden çeşitli koşullarda oluşan karbenler“nötral-elektrof il”ara ürünler oldukları için nükleofil gücü karbonil tarafından azaltılmış olan a,p- konjuge karbonil bileşikleriyle direkt katılma ürünü vermekte zorlanırlar. Bu nedenle, çalışmada a, P- konjuge karbonil bileşiklerine katılma reaksiyonunu gerçekleştirmek amacıyla, öncelikle indirekt bir yöntem olan karbonil bileşiklerini asetal/ketalleştirme reaksiyonları gerçekleştirilerek, bu bileşiklerin bir diazo bileşiği olan dimetil diazomalonat (dmdm) ile verecekleri reaksiyonlar incelenmiştir. Reaksiyonların elektrofilik sikloprapanların sentezi için uygun bir indirekt yöntem olup olmadığı araştırılmıştır. Çalışmada çıkış bileşikleri olarak krotonaldehit, sinnamaldehit, p-ionon, a-ionon ve siklopentanon kullanılmıştır. Bu aldehit/ketonlara uygulanan asetal/ketalleştirme reaksiyonlarının ardından, elde edilen asetal/ketal türevlerinin dimetildiazomalonat bileşiği ile reaksiyonları gerçekleştirilmiştir. Sinnamaldehit ve krotonaldehit etilenasetallerinin diazo bileşiği ile reaksiyonları sonunda siklopropan ürünleri düşüki verimle; bunun yanı sıra [2, 3] -sigmatropik göç ve C-Q insertion ürünleri daha yüksek verimle elde edilmiştir. ot- ve p- ionon etilenketallerinin reaksiyonlarında ise ağırlıklı ürün f_2, 3] -sigmatropik göç ürünü olmuştur. Amaçlanan siklopropan ürünü ancak siklopentenon etilenketal bileşiği ile gerçekleştirilen reaksiyonda yüksek verimle elde edilmiştir. -vı-
Özet (Çeviri)
5UMHARY THE REACTIONS OF UNSATURATED CARBONYL COMPOUNDS AND THEIR DERIVATIVES WITH DIAZO COMPOUNDS conj in cycl fünc carb enol pres homo“dim Under thermal, photolytic and catalytic conditions, ugated carbonyl compounds react with diazo compounds various ways. These include the 1,3-dipolar oaddition reactions of metal-carbenoids to carbonyl (Scheme-1); insertions of present C-H, aldehydic C-H, (Scheme-2); additions to the (epoxidation) (Scheme-3); rearrangements; carbene tions (1 ;3-dioxoles) ene/carbenoids to the ic 0-H, and C-C bonds ent c=Q bonds logations; Wolff erizations”and formation of new olefins. o-«- /COCH3 :C COOR / O +. +cf NCH, \ COOR DtS Scheme 1. The 1,3-Dipalar Cycloaddition Reaction Of Metal-Carbenoid To Carbonyl Function. Cyclopropane derivatives, activated by two or more electron-withdrawing substituents are classified as electrophilic cyclopropanes, which are very useful intermediates in organic synthesis. A direct synthetic approach to these cyclopropanes may include the reaction of enones with diazo compounds as carbene/carbanoid precursors. But cyclopropanation generally fails due to the, electron-poor character of the enones, although a few successful examples can be found in the literature. There are some reports of electrophilic cyclopropane synthesis via the reaction of enones with reagents other than diazo compounds. These routes ware also unsuccessful with several enones. -vii-R1\ O + c: R1, \ / CH R2 <0^ + /c RZ R1 R2 \6 C «a**** Scheme 2. Insertions Of Carbene/Carbenaids Ta The Present C-H, Aldehydic C-H, Enalic D-H, And C-C Bands. /,c=o RV R2 Vo / \ / C /\ R1 R2 Scheme 3. Addition To The Present C=D Band. One of the indirect methods af cyclopropanation of enones was presented by Mash and coworkers. The method included protection of ketones by ketalization with threitol, cyclopropanation of the double bond with Simmons-Smith reagent, and deprotection of the ketone function, finally yielding cyclopropane derivatives with only one electron-withdrawing substituent. -viii-Another indirect method included the synthesis of electrophilic cyclopropanes by the photolysis of corresponding 1-pyrazolines, the latter being available via the 1,3-dipolar cycloadditian of diazoacetaldehyde dimethyl acetal to enones. Diazomethane mas also used as the 1,3-dipole. In both cases, the aldehyde function was reproduced by hydrolysis. In a similar work, stable methylene pyrazolines mere obtained from the reactions of ailene carboxylates and diazomethane. But the thermal decompositions of these pyrazolines yielded methylene cyclopropane derivatives in trace amounts only. In order to synthesize the electrophilic cyclopropanes using protection-cyclopropanation- deprotection sequence the common ketal derivatives instead of tHreitol ketal might be used as starting compounds. Only a few reactions studied by Doyle group could be found in the literature. Doyle and co-workers reported results of transition metal catalyzed reactions of diazo compounds with allylacetals (acrolein acetals) and thioketals that provided a simple route to synthetically useful multifunctional organic compounds. The synthetic versatility of this class of polyf unctianal compounds has been examined with selected transformations. In the catalytic reactions of allylacetals with diazo esters the possible routes were cyclopropanation, C-0 insertion and \Z, 3] - slgmatropic rearrangement. These mechanisms were presented as shown below. X N,C. CH(OR% Rt)CH=CH- R I -CH- f COOR2 C- COOR2 OR1 [2,3]-Sigmatropic Rearrangement (Rt>),CH Z COOR2 Cyclopropanation CH- C- COOR2 OR1 OR1 C-0 Insertion R2OOC COOR2 R200 Dimerization COOR2 + Other products -ix-In his study Doyle studied with only two kinds of allylacetals (acrolein and cinnamacetals ). In order to increase the number of examples and to gain more information about the reaction mechanisms, much more enone acetals had to be examined. In our study, crotonaldehyde (1), cinnamaldehyde (2), prionone (3), a-ionone (k) and cyclopentanone (5) were used as starting of these conjugated carbonyl compounds. The ethylene acetal/ketal derivatives of enones were synthesized in order to deactivate the conjugated carbonyl functions. These enone acetal/ketals were reacted with dimethyl diazomalonate in the presence of copper (II) acetylacetonate. As the formation of carbene dimerization by product was dependent on the rate of addition of diazo compound, their presence could be virtually eliminated by proper choice of addition time- The consumption of diazo compound present in the reaction mixture were examined by GC analysis of the continuing reaction. Reaction products were analyzed by GC, TLC and were purified by column and/or preparative-TLC chromatographies. The purities of the compounds obtained were recontrollerl by GC. The compounds were identified by IR, GC-Mass, H-NMR and C-NMR spectroscopies. The acetals la and 2a of crotonaldehyde and cinnamaldehyde yielded expected cyclopropanes lb and 2b in low yields, and [2 >^3 -sigmatropic rearrangement products lc and 2c, C-0 insertion products Id and 2c as major compounds. The ketal 3a of P-ionane yielded [2, 3] - sigmatropic rearrangement product 3c and the unexpected product 3d. In the reaction of the ketal ^a from a- ionone, the obtained product was only \Z, Zj -sigmatropic rearrangement product kc and on the other hand, in the reaction of the ketal 5a from cyclopentanone, the product was cyclopropane 5b and the hydrolyzed derivative of it. The products lb, lc, Id, 2b, 2c, 2d, 3c, kc, 5b were orginals. R1 R2 HO OH ethylortofbrmat NH.CI 12,3,4 1 : R*CH3 ; R2:H (crotonaldehyde) 3:R1>^S>_w ' R2:CH3 (P-|onone> M- ^20 R2 O- 1a,2a,3a,4a 2: R^Ph ; R2:H (cinnamaldehyde) 4:ri- ^ ; R2:CH3 (a-lonone) - x-r,^x°} + <l ssr RV<tO + sJ r2 b-1 z I Z R2 5a R2 1a,2a,3a,4a 1b,2b,3b 1c,2c,3c,4c /~\ O O J-^T* 1d,2d 3d Ö O z r\. _ <r\> q Ö * < S QxS + (İxî 5b 5c -xi-
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