Tetraaminoalkenler (elektronca zengin olefinler)
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Dosyalar
Tarih
1993
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
İnönü Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışma özellikle benzimidazol ve benzeri halka içeren elektronca-zengin olefinlerle (e.z.o.) ilgilidir ve üç bölümden oluşmuştur. Birinci bölümde e.z.o. ' lerle ilgili ve başkalarınca yapılmış çalışmalar değerlendirilmiştir. İkinci bölüm e.z.o. ' lerin sentez yöntemleri ve bazı tepkimeleri ile ilgilidir ve üç alt bölüme ayrılmaktadır. a) Benzimidazol çekirdeği içeren yeni 2 tipi e.z.o. 'lerin sentez edilmeleri ve bazi özelliklerinin araştırılması. R f l°I X I°J R R 2a R,R'=Me 2b R,R'=Et 2C R=Me;R'=Et 2d R,R»=Bz 2e R=Me,R'=Bz 2 Tipi e.z.o. ' lerden 2a, 2b ve 2c çok yüksek verimle sentez edildi. DiŞer taraftan, benzil grupları nedeni ile 2d ve 2e e.z.o. ' leri izole edilemezken bunların debenzilasyon ürünleri 3d, 4d ve 3e izole edildi. N,N'-dibenzil-o-fenilendiaminin bis(dimetilamino)-t-bütok- simetan ve alkollü KOH ile etkileştirilmesinden sırasıyla 5 ve 6 nolu bileşikler ele geçti. R O Bz \y^f Bz Bz «NCBO I Bz 3d R=Bz 3e R=Me 4d R=Bz 2 tipi e. z. o. 'ler in havada kendiliğinden tutuşarak yandığı ve kemilüminesans özellik gösterdiği saptandı. 2 tipi e. z. o. 'ler 6A-elementleri(0, S, Se, Te), PhNCS, PhNCO, CS2, metil iyodürlü CS2, Ag[BF4], [{RhCl(COD) }2], CH3CN ve dimetil fosfit ile etkileşererek sırasıyla 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 ve 21 nolu bileşikler sentez edildi. N- R 0 ıı ?C -N ı 10a R,R'=Me; X=0, S, Se, Te 10b R,R'=Et; X=0,S,Se,Te 10c R=Me,R'=Et; X=S,Se,Te lOd R,R'=Bz; X=S İla R,R'=Me 11b R,R'=Et İle R=Me,R'=Et lld R,R'=BZ 12a R,R'=Me 12b R,R'=Et O it s II C-S-Me Me-S-C L2 BF4 ] 13 R=Me 14 R=Et 15 16a R,R'=Me 16b R,R'=Et 16C R=Me,R'=Et.Nv |0| \r1iCC0D)C1 Me MCI 13 L CH2CN 17 18 19 R=Me 20 R=Et (OMe)9 0/ Me "/ Me i P. i MeH Me 21 b) Benzotiyazol çekirdeği içeren ve trans yapıya sahip 7 e.z.o. 'i kullanılarak 22, 24 ve 25 nolu bileşikler sentez edildi. Ayrıca 7 e.z.o. 'nin benzeri olan ancak cis yapıya sahip 9 e.z.o. *i ilk kez sentez edilerek fiziksel ve spektoroskopik özellikleri belirlendi. V7N^ / \, sV ®M® 3 o V Me Me O Me j5-(OMe>2 Me to Me 22 24 25 c) Yeni e.z.o. 'ler 2a ve 2b ile 35,36a ve 36b e.z.o. ' lerinin benzoin ve asetoin tepkimelerindeki katalitik etkileri araştır a İdi. I 1 Bz Bz R R AA ı R R 35 36a R,R'=Bz 36b R=Et,R'=Bz Bu katalitik tepkimeler sonucunda 2a ve 2b benzaldehit, anisaldehit, 4-tolilbenzaldehit, salisaldehit ve furfuralı benzoin ve benzoin analoglarına yüksek verimle dönüştürdüğü saptandı. Diğer taraftan 35,36a sıcaklığında asetaldehiti kanıtlandı. ve 36b e.z.o. 'ler inden 3 6a oda 50 verimle asetoine çevirdiği CH3CHO ArCHO 36a HO 0.H3C-C-Ü-CH3 HO 0 ! II. Ar-C-C-Ar Son bölüm ise yeni bileşiklere ait 1H-nmr, 13C-{1H}-nmr, 13C- ^-H-mnr, 13C-{1H} -nmr (spin-echo), 31P-{1H}/ 15N-{1H}/ 103Rh-{1H}- nmr, FTIR, kütle spektrumları, element analiz ve en ya da kn verileri, 2a bileşiği ve 16a bileşiğine ait X-ışınları spektrum verileri ile elde edilen bütün sonuçların tartışmasını içermektedir.
This work particularly deals with electron-rich olefins(e. r.o. ) which have benz imidazole and related rings and consists of three chapter. In the first chapter; work with e.r.o.'s done by previous research workers is considered. The second chapter is concerned with synthesis methods and some reactions of e.r.o.'s, and is divided into three subchapters : (a) The synthesis, investigations and some properties of new e.r.o.'s of 2 type which contains benzimidazole kernel. R R 2a R,R'=Me 2b R,R«=Et 2 o R=Me;R'=Et 2d R,R'=BZ 2e R=Me,R'=Bz Among the e.r.o. 'sof 2 type, 2a, 2b and 2c were synthesized in high yields. On the other hand, due to presence of benzyl groups, 2d and 2e e.r.o. 's could not be isolated but debenzylated derivatives; 3d,4d and 3e were obatained instead of the e.r.o. 's. From the reaction of N,N'-dibenzyl-o-phenylenediamine with bis(dimethylamino)-t-butoxymethane and alcoholic KOH were obtained compounds of 5 and 6, respectively. 3d R=Bz 3 e R=Me 4d R=Bz XIX It has been found out that the e.r.o.'s of 2 type spontaneously inflames in air and shows chemiluminesence. Through the reaction of the e.r.o. 's of 2 type with the 6A- elements(0, S, Se,Te), PhNCS, PhNCO, CS2, Ag[BF4], [ {RhCl (COD) }2], CH3CN, and dimethyl phosphite were synthesized compounds of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21, respectively. 10a R,R'=Me; X=0, S, Se, Te 10b R,R'=Et; X=0, S, Se, Te 10c R=Me,R'=Et; X=S,Se,Te lOd R,R'=Bz; x=s lla R,R'=Me lib R,R'=Et lie R=Me,R'=Et lid R,R'=Bz 12a R,R'=Me 12b R,R'=Et R (°IK:Iq [2BF4_] 13 R=Me 14 R=Et 15 16a R,R'=Me 16b R,R'=Et 16c R=Me,R'=Et Me JOT \r!iCC0D)C1 I Me RhCl 1 CH2CN 17 18 19 R=Me 20 R=Et XX (OMeV 0/ Me y Me MeH ike 21 (b) Compounds of 22, 24 and 25 were synthesized using the e.r.o. of 7 which has benzothiazole kernel and trans-structure. In addition, e.r.o. of type 9 which analogue compound to 7, but has cis-structure was synthesized first time and determined physical and spectroscopic properties. ^sV\v O Me Me Me ^-(0Me)2 22 24 25 XXI (c) The catalytic effect on the benzoin and acetoin reactions of the new e.r.o.'s of 2a and 2b and e.r.o.'s of 35, 36a and 36b were investigated. R,NE Bz Bz / R R i i W \ R i R 35 36a R,R'=Bz 36b R=Et,R'=Bz It has been fixed that, using the olefins of 2a and 2b as a catalyst, benzaldehyde, anisaldehyde, p-tolilbenzaldehyde, salisaldehyde and furfural were converted to benzoin and benzoin analogues with high yields. On the other hand, it has been proved that, only 36a from e.r.o.'s of 35,36a and 36b was converted acetaldehyde to acetoin with 50 % yield at room temperature. HO 0 CH3CH0 -^^^C-C-C-CH, ArCHO HO 0 I II Ar-C-C-Ar The last chapter contains x-ray spectrum data of 2a and 16a and^-H-nmr, 13C-{1H}-nmr, 13C-1H-nmr, 13C-{1H}-nmr (spin-echo), 31P- {%}, 15N-{1H}, 103Rh-{1H}-nmr, FTIR, mass spectrums, micro analysis and melting or boiling points data of all new compounds and contains their discusion with all results have been obtained.
This work particularly deals with electron-rich olefins(e. r.o. ) which have benz imidazole and related rings and consists of three chapter. In the first chapter; work with e.r.o.'s done by previous research workers is considered. The second chapter is concerned with synthesis methods and some reactions of e.r.o.'s, and is divided into three subchapters : (a) The synthesis, investigations and some properties of new e.r.o.'s of 2 type which contains benzimidazole kernel. R R 2a R,R'=Me 2b R,R«=Et 2 o R=Me;R'=Et 2d R,R'=BZ 2e R=Me,R'=Bz Among the e.r.o. 'sof 2 type, 2a, 2b and 2c were synthesized in high yields. On the other hand, due to presence of benzyl groups, 2d and 2e e.r.o. 's could not be isolated but debenzylated derivatives; 3d,4d and 3e were obatained instead of the e.r.o. 's. From the reaction of N,N'-dibenzyl-o-phenylenediamine with bis(dimethylamino)-t-butoxymethane and alcoholic KOH were obtained compounds of 5 and 6, respectively. 3d R=Bz 3 e R=Me 4d R=Bz XIX It has been found out that the e.r.o.'s of 2 type spontaneously inflames in air and shows chemiluminesence. Through the reaction of the e.r.o. 's of 2 type with the 6A- elements(0, S, Se,Te), PhNCS, PhNCO, CS2, Ag[BF4], [ {RhCl (COD) }2], CH3CN, and dimethyl phosphite were synthesized compounds of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 21, respectively. 10a R,R'=Me; X=0, S, Se, Te 10b R,R'=Et; X=0, S, Se, Te 10c R=Me,R'=Et; X=S,Se,Te lOd R,R'=Bz; x=s lla R,R'=Me lib R,R'=Et lie R=Me,R'=Et lid R,R'=Bz 12a R,R'=Me 12b R,R'=Et R (°IK:Iq [2BF4_] 13 R=Me 14 R=Et 15 16a R,R'=Me 16b R,R'=Et 16c R=Me,R'=Et Me JOT \r!iCC0D)C1 I Me RhCl 1 CH2CN 17 18 19 R=Me 20 R=Et XX (OMeV 0/ Me y Me MeH ike 21 (b) Compounds of 22, 24 and 25 were synthesized using the e.r.o. of 7 which has benzothiazole kernel and trans-structure. In addition, e.r.o. of type 9 which analogue compound to 7, but has cis-structure was synthesized first time and determined physical and spectroscopic properties. ^sV\v O Me Me Me ^-(0Me)2 22 24 25 XXI (c) The catalytic effect on the benzoin and acetoin reactions of the new e.r.o.'s of 2a and 2b and e.r.o.'s of 35, 36a and 36b were investigated. R,NE Bz Bz / R R i i W \ R i R 35 36a R,R'=Bz 36b R=Et,R'=Bz It has been fixed that, using the olefins of 2a and 2b as a catalyst, benzaldehyde, anisaldehyde, p-tolilbenzaldehyde, salisaldehyde and furfural were converted to benzoin and benzoin analogues with high yields. On the other hand, it has been proved that, only 36a from e.r.o.'s of 35,36a and 36b was converted acetaldehyde to acetoin with 50 % yield at room temperature. HO 0 CH3CH0 -^^^C-C-C-CH, ArCHO HO 0 I II Ar-C-C-Ar The last chapter contains x-ray spectrum data of 2a and 16a and^-H-nmr, 13C-{1H}-nmr, 13C-1H-nmr, 13C-{1H}-nmr (spin-echo), 31P- {%}, 15N-{1H}, 103Rh-{1H}-nmr, FTIR, mass spectrums, micro analysis and melting or boiling points data of all new compounds and contains their discusion with all results have been obtained.
Açıklama
Anahtar Kelimeler
Kimya, Chemistry
Kaynak
WoS Q Değeri
Scopus Q Değeri
Cilt
Sayı
Künye
Küçükbay, H. (1993). Tetraaminoalkenler (elektronca zengin olefinler). Yayımlanmış Doktora lisans tezi, İnönü Üniversitesi, Malatya.
