Polioksoaldehitlerin azidinyum tuzlarıyla reaksiyonları
The reaction of polyoxoaldehydes with azidinium salts
- Tez No: 46575
- Danışmanlar: PROF.DR. OLCAY ANAÇ
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1995
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 70
Özet
ÖZET Bu çalışmada iki farklı (3,8-dioksoaldehit karşılık gelen y-piron bileşiklerinden hazırlanmıştır. Bir p\y-dioksoaldehit olan etil 2,4-diokso-butanoat etil piruvattan başlanarak hazırlanmıştır. Yine bir P,y-dioksoaldehit olan 2-okso- butandial'in türevi 4,4-dimetoksi-3-oksobutanal, l,l-dimetoksi-2-propanon'dan başlanarak hazırlanmıştır. Adı geçen bu bileşikler, sodyum asetatlı ortamda 2- azido-1-etilpiridinyum tetrafloroborat ile diazo transferi reaksiyonuna sokulmuştur. 3,8-dioksoaldehit bileşikleri olan 5-fenil-3,5-dioksopentanal ve 3-oksopen- tandial'in reaksiyonlannda deformilasyonlu ve deformilasyonsuz diazo transfer ürünleri gözlenmiştir. Ayrıca 3-oksopentandial'in reaksiyonunda iki kat deformi- lasyon da gerçekleşmiştir. Bu ürün ayrıca bağımsız bir yoldan sentez edilmiştir. |3, ö-dioksoaldehitlerin hazırlanmaları sırasında, bazik ortamda bir aldehit grubunun kopması sonucu l-substitue-l,3-butandion'lar da oluşmaktadır. Diazo transferinde bu yan ürünlerin de diazolandığı görülmüştür. 4,4-dimetoksi-3-oksobutanal diazo transferi sırasında deformilasyon sonucu tek ürün olarak l-diazo-3,3-dimetoksi-2-propanonelde edilmiştir. Etil 2,4-dioksobutanoatm Claisen kondenzasyonu ile hazırlanması sırasında ayrılamaz karakterli yan ürünlerin de oluşmuş olması ihtimali vardır. Diazo transferi sonucu en az 6-7 diazo bileşiğinin oluştuğu gözlenmiştir. Bu reaksiyonun ayrım ve analiz çalışmaları halen sürmektedir. VII
Özet (Çeviri)
SUMMARY THE REACTION OF POLYOXOALDEHYDES WITH AZTOINTOM SALTS Because of their various kind of reactivities the diazo compounds, whose general formula is shown below, have been one of the important research areas of organic chemists. R-O-R R- C-R R-C-R +N «- +N -- n: ii m H -N: N +n Diazo compounds constitute an interesting class of organic compounds, which are the main precursors of carbenes and carbenoids. R-C-R f^y°r» R-C-R +N, 11 catalysis ~ These diazo compovmds serve organic chemists not only as carben- carbenoid precursors, but also as valuable synthetic intermediates. ot-Diazo-p-oxoaldehydes, which were represented in the literature only with three examples until last year, have been succesfully synthesized by a rather general method in 1994 by Sezer and Anaç (scheme 1). « H R-C-CH=N2 T --2 -? -?- ff j + | I BF4 O 0.^0 K^ +R-ç-Ç-CHO Et Scheme 1: Synthesis of a-cfiazo-p -oxoaktehydes. II II 0 Ng It is thought that the success of the nondeformylating diazo transfer can be applied to the synthesis of bis(diazo)polyoxoaldehydes and polyoxodiazoal- dehydes. VHlThus 5-phenyl-3,5-dioxopentanal and 3-oxopentandial, which are f},8- dioxoaldehyde compounds were synthesized from the appropriate y-pyron compounds (scheme 2). R-C-CH-CO-CH-CHO ii.. L O -H-COO“ R-C-CH-C-CH, R-C=CH-CO-CH=CH-OH i O. t-H R-C=CH-CO-CH==CH-0 i O il O O +AcOH R-C-CHo-C-CI-U-C-H II ^11 ^ II R-C-CH0-C-CH3 11 ^11 -* O O H H 1 \ 1 it 1 cvo,H”o H M +2 CH3COONa 11 1 + CH,COONa °-H'° Scheme 2: Mechanism of the ring opening reaction of y-Pyron derivatives. These compounds were diazotized with 2-azido-l-ethylpyridinium tetrafluoroborate in the presence of sodium acetate. As a result of these reactions deformylating and nondeformylating diazo transfer products were obtained (scheme 3). It was also observed that there was two-fold deformylation in the reaction of 3-oxopentandial (scheme 3). This product was also synthesized by an independent method. For this purpose, l,5-bis(N-methyl-N-phenylamino)- trans,trans-l,4-pentadien~3-on was synthesized from y-pyron (scheme 4). Then this compound was reacted with tosylazide and two-fold deformylating diazo transfer product of 3-oxopentandial, which is l,3-bisdiazo-2-propanon, was obtained (scheme 5). IXo 1)2 OH.». AcO + FrSr 2)2AcOH RCO-CH2-CO-CH2-CHO (+ RCO-CH2-COCH3) R=H, Ph R-C-C-C-C-CHO II II II II O N20 Fi, O M + R-CO-CH C-CHO \ 11 N-N H (or other tautomers) Et N, R-C-C-C-CH=N2 II II II ^ O N2O r+ R-C-C-C-CH, II II II 3 O N20 + N2=CH-C-CH=N2 1+ N2=CH-C-CH3 O \ / (only for R=H) Scheme 3: Products of the transdiazotization of 3-oxopentandial and 5-phenyl-3,5-dioxopentanal. O O 2HI< O Me Ph İJ22. MeN Ph' N Me >h Scheme 4: Synthesis of 1,5-bis(M-methyl-N-phenvlamino>-tfans.tfans- 1,4-pentadien-3-on. M^ Ph' J* N Me f >h TosNo 03^ Et BF4 ' decomposition Me +Tos-N=CH- Nx + N2=CH-C-CH=N2 Ph 0 Scheme S: The reaction of 1,5-bis (N-methyi-N-phenyiamino) trans. trans- 1.4-pentadien-3-on with azides. xMoreover 4-oxo-2-butanon side products were formed from the cleavage of one of the formyl groups during the synthesis of p\8-dioxoaldehydes in basic medium. These side products were also diazotized by the azidmium salts. 4,4-dimethoxy-3-oxoaldehyde, which is a p,y-dioxoaldehyde derivative, was prepared from l,l-dimethoxy-2-propanon (scheme 6). Afterwards this compound was diazotized with 2-azido-l-ethylpyridmium tetrafluoroborate in the presence of sodium acetate. As a single product l-diazo-3,3-dimethoxy-2- propanon was obtained via deformylation during the diazo transfer (scheme 7). CHg-CO-CKOCH^ + HCOOCH3 N300*^» [QHC-CH-CO-CH(OMe)j“ Na+ AcOH -2CH3OH OHC-CHj-CO-CHpMe^ + NaOAc Scheme 6: Synthesis of 4,4-dimethoxy-3-oxobutanal. OHC-CH2-CO-CH(OMe)2 + O 1 -ACQ* l^^CH-CQ-CKOMe^ +,r N3 Et + OHC-CNz-CO-CKQMe^ Scheme 7: The reaction of 4,4-dimethoxy-S-oxo-butanal with 2-azido-1-ethylpyricflnium BF4. Ethyl 2,4-dioxobutanoat, which is also a {3,y-dioxoaldehyde was generated from ethylpyruvate. There was a probability of formation of unseparatable side products during the Claisen condensation (scheme 8). Ethyl 2,4-dioxobutanoat was diazotized with 2-azido-l-ethylpyridinium tetrafluoroborate in the presence sodium acetate (scheme 9). It was observed that at least 6-7 diazo compounds were formed. The separation and analysis are still going on. XICH3- CO-COOEt I - EtO -EtOH [ ”CIV-CO-COOEt ] CbU-C-Ct OEt OHC-CH2-CO-COOEt I OHC-CH-CO-COOEt (target product) CHfİS-0 ÇO-COOEt *OEt I CO + EtO + CH3- CO-CH2-CO-COOEt CHg-CO-CH-CO-COOEt O CH3-CO-C-CH2-CO-COOEt OEt | CH3-CO-CO-CH2-CO-COOEt.1 CH3-CO-CO-ÇH-CO-COOEt Scheme 8: Mechanism the Claisen condensation of ethyi 2-oxopropanoat with ethyl formate, and probable products. CH3-CO-COOEt OHC-CH2-CO-COOEt CH,-CO-CO-CH,-CO-COOEt CHg-CO-CHs-CO-COOEt AcO^ OHC-C-CO-COOEt II N2=CH-CO-COOEt OHC-CH=N2 CH3-CO-CO-CH=N2 N2=CH-CO-COOEt CHg-CO-CO-CH-CO-COOEt II N2 CH,-CO-C-CO-COOEt.5 It CH3-CO-CH=N2 Scheme 9: Probable products of diazotization of the Claisen products of ethyl 2-oxopropanoat. XII