Polimerik tosil hidrazon kullanarak ayrıştırma reaksiyonları
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- Tez No: 55603
- Danışmanlar: DOÇ.DR. OYA ATICI (GALİOĞLU)
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Ayrıştırma, Tosilhidrazon, Decomposition, Tosylhydrazone
- Yıl: 1996
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
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Özet (Çeviri)
SUMMARY DECOMPOSITION OF POLYMER1C HYDRAZONE Aldehydes and ketones can be converted into corresponding alkenes ör bicyclo (n. 1.0.) ring systems by treating their tosyl hydrazone derivatives with strong base. This method has considerably been used in recent years and given rather good results. These reactions are called as Bamford-Stevens reactions. in this method, p-toluen sulfonyl hydrazones (tosyl hydrazones) of the ketones ör aldehydes are first obtained, then the diazo compound is formed by elimination of p-toluen sulphinate anion from tosyl hydrazone in a strong basic medium at high temperature ör by photochemical reaction of tosyllhydrazone. As shown in the scheme below, if the decomposition are carried out in aprotic solvents, the reaction proceeded through a carben intermediates \vhereas the decomposition under protic conditions leads to the formation of products via diazonium and /ör carbonium intermediates.Na+ /s~^\baS6“. - NaTs -C-N=N-S02-(O/ Ch^*”-C=N-N-Ts -^4* -C=N=N | ^\-/ll Protic »_C_H^ ^ + _cLH -H* » products solvent,^Nl -(Jİ-NSN:diazonium ioncarbonium ion -C=N=N l AProtic» ^ + -c:^ products solventcarben Polymeric reagents are also used in organic reactions. Polymeric reagents are more advatages than organic reagents. Öne of the advantages of using polymeric reagents, is that they are easily separatable, by simple filtration ör centrifügation from having compounds low-moleculer-weights when studied with insoluble polymers, by ultrafiltration when studied with soluble polymer. These reagents also often lack many inconvenient proporties of the corresponding low-moleculer-weighted reagent, such as lability, volatility, toxicity ör odor. in this work, thermal decomposition of tosylhydrazones and polymer bounded sulphonyl hydrazone of cyclohexyl phenyl ketone have been studied in the presence viof a strong base with aprotic and protic solvent. in order to find out ifa improvement in product yields and distribution are achieved ör not by the polymer support. Cyclohexyl phenyl ketone were readily converted to corresponding tosyl hydrazone with tosylhydrazine in acidic methanol (recrystallized from methanol, yield 83-92%, m.p.: 107-108°C). The FTIR spectral properties of cyclohexyl phenyl ketone tosyl hydrazone were, vmax = 3345, 1327,1165 cm“. ONNHTs r^^r- J-rXXs| NH2NHTs|f::^r~^~rX>Xl LS^ k^/J pH=3.5, methanol ^^ ^S Polymeric reagents, resins, consisting of cross-linked poly (styrene-co- divinylbenzene) matrics functionalized with sulfonyl hydrazine group was used in our study. Resins were readily converted, to the intermediate poly(styrene-co- divinylbenzene) sulfonylchloride by refluxing in a solution of phosphor pentachloride in dichlormethane. Then the reaction of the polymer with cyclohexyl phenyl ketone in refluxing methanol gave the corresponding hydrazone derivative. The polymeric reagents showed typical spectral vibrations, v^* = 3325, 1370, 1310, 1150 cm”. fc^-sc* pc^ffA. Q-©-aoft -ÜMÜ» A S02NHNH2 O+ Or^~O“* ©-X^-S°2NHN=f~ SO2NHNH2V-V in the subsequent decompositions N-methyl pyrrolidone and ethylene glycol were used as aprotic and protic solvents. On the other hand sodium methoxide and sodium |3-hydroxy ethoxide were prefifered as strong bases. Both bases NaOCH3 and sodium p-hydroxy ethoxide were prepared by dissolving metalic sodium in absolute methanol and ethylene glycol respectively. After decomposition, remaining the presence of unreacted tosylhydrazone has - ahvays been checked. Reaction yields were based on the starting ketone ör tosylhydrazone derivatives. Identifıcation of the reaction products have been achieved by using, GLC (gas liquid chromatography), TLC (thin-layer chromatography), GC- viiMS (gas chromatography-mass spectroscopy), FTIR (infrared spectroscopy), UV (ultraviole spectroscopy), NMR (nuclear magnetic resonans). Decomposition of tosylhydrazones derivated from cyclohexyl phenyl ketone was found to produce a mbcture of product. The results have been summarized in Table 1. As shown table l, öne of the products was benzyl cyclohexan (product 1). The product was probably formed by the effect of parent tosyl hydrazone, free sulphonic acid groups methanol ör acid side of in exchange resin. The spectral proporties of benzyl cyclohexane were, FTIR,vmax = 3080, 3060, 2926, 2853, 1599 cm'1, 'H-NMR (CDC13), 8 2.2 (2H, doublet), El, m/z = 173(38) (molecular ion), 115(5.1), 92(100), 83(45.5), 67(11.5). Reaction mechanism was shown below. -C=N-NKTs ba36> -(&N^frTs.*-*-C-N=NTs-^-GrjNNN: |l l ”“l ”“ J -TsOR1^ r^VC<K”, H- ^e -J [C J] l l Benzyl cyclohexane s - C-H««Ç:B «.-*-. ^^“XX1 (Product 1)ll Another product in decomposition was identified as benzal cyclohexane (product 2) which can be an expected either by rearrengement of carbenic intermediate ör hydrogen elimination from intermediate carbonium ion. The spectral proporties of benzal cyclohexane were, FTIR,vmax = 1653, 1495, 1074, 918, 841, 737, 699 cm'1, 'H-NMR (CDC13), 8 6.1 (H, singlet), El, m/z = 172(94.1) (molecular ion), 157(7), 143(33.1), 129(74.8), 115(97.5), 104.1(88.5), 91(82.2), 81(100), 65(24.8). Reaction mechanism was shown below. â<Pî6 Benzal cyclohexane1- benzyl cyclohexene (Product 3) -(Product 2) H i The third product was 1-benzyl cyclohexene (product 3) which was derivatived from benzal cyclohexane by hydrogen migration. The spectral properties of 1-benzyl cyclohexene were: FTIR,vmax = 1653, cm”1, ^-NMR (CDC13), 8 3.2 (2H, singlet), 5.4 (H, triplet), El, m/z = 172(97) (molecular ion), 143(27), 129(65.2), 115(45), 104.1(61.4), 91(100), 80(86.1), 65(44.3). l-Phenyl cycloheptene was an another decoposition product. l-Phenyl cycloheptene was formed by carbon skeleton enlargement in a carbenoid ör viiilI U > I I I I I I l I I &£QfJ* TT<8-o5r ila rj ı-ı oo ...“ röit1 s s s s.. - R jüf -. «o o.I B---.Swf» 0”|« ^f- cM t-- in 13°“T_ -f ”*. °.“”i °9 ^Ol K ö ö ö c» ı 2 °° «sl ~ * uol N/-v S. 5( ) °?.ÖV^/ f« 0\ <sf »O -«t ^>T u| cx5 >n »-ı tsj â/^SStl..»o'ı-î ' ' ö ö VQ m g>>^J/Ş -ı m 3' ı^7^ §§ jö^îl? <* * S ^ Qo o-o-ı &e | oo »o .“; ı ı §S /PfcP! «s ^' '. 2; S JHw \-yls* <-ı m l»g^*c y-v S^-.|^pW|i °° -.g^t-C_ B-E **! °^ Syfc=^ n£ in f-.-'.-ı oo vo t~ «-' T3Y=y! ^ CS -ı CN» r-H |*!P|I. - - u/^£1 '”i °. ^ ^ ÖvLJ/e£ »O ^O O -^-S t~~ VO «O ux=y^ ^H (s, (N V ^fi-'ü ^o es f- 1Ö'g--nt~;C*1»O 8A'^'&t TT T|- O ı-ı »O O\ »O l İOf - <N - C* lJX13 ^ **. °°- ^ aS 3 ^ ö ^ ö <3_o-S -S :-s.2 s S s.2 ^ S e s||||İ||| SA^3'°J3A5'°^ oOKP-ıMOW&-ıW p7^~^ -ğ -a ^;§ S § § l | «c^ B © § a*'l l ^ o l ıl l a a ili Iii HOÜHHco-<2GOp-,,? ixcarbonium system. The spectral properties of this product were: FTIR.Vma* = 1597, 1078, 1028, 969, 965, 853, 754 cm1, 'H-NMR (CDC13), 8 2.34 (2H, quartet), 2.64 (2H, triplet), 6.12(H, triplet), EI, m/z = 172(71.3) (molecular ion), 143(15.3), 129(52.2), 115(39.5), 104. 1(100), 91(57.3), 81(60.5). Forming of the product of rection mechanism is shown below. -CO 1 -Benzyl cycloheptene (Product 43) sec. carbonium tert- carbonium -H* The remaining two products were methoxy, cyclohexyl, phenyl methane and 0- hydroxy ethoxy, cyclohexyl, phenyl methane. These products were formed by the reaction carbonium ion with nucleophile(base). The reaction mechanism is shown below. =N=N:+ROH Methoxy cyclohexyl phenyl methane (Product 4i) OOfeChfeOH i^O ?**««- g^o p-hydroxy ethoxy cyclohexyl phenyl methane (Product 6)The spectral properties of methoxy cyclohexyl phenyl methane were, EI; m/z = 204.1(15.9)(rnolecularion), 129(13.4), 105(51.6), 91(89.2), 77(84.1), 65(17.2), and p-hydroxy ethoxy cyclohexyl phenyl methane, FTIR,vmiuc = 3404, 3063, 3028, 2926 2852, 1602, 1263, 1053 cm'1, ^-NMR (CDC13), 8 1.1 (H, multiplet), 3.4 (4H, multiplet), 3.6 (H, triplet), 3.9 (H, doublet), 13C-NMR (CDC13), 8 129.2,127.4 Ar -C, 70.8 C-O, 62.1 CH20, 44.4 CH2OH, 29.6, 29.4, 26.4, 24.1 ring C, EI, m/z - 151(100), 107(78.9), 91(24.7), 79(28. 9), 5 5 (5. 5), 45(9). Cyclohexyl phenyl ketone (Product 5) were also formed in our study. The spectral properties were the same with the cyclohexyl phenyl ketones. FTIR, v,^ = 3061, 3026, 2952, 2854, 1683 cm"1, !H-NMR (CDCI3), 8 1 (2H, multiplet), 3.25 (H, multiplet), 7.2 (Ar-H, multiplet), EI, m/z = EI, m/z = 188(10.9) (molecular ion), 133(8.9), 120(5.73), 105(100), 77(42), 55(12.1), 41(10.2), UV, AT, 214, 238. Dimer products were also formed in our study. Expected products such as benzal cyclohexane, 1 -benzyl cyclohexene and 1 -phenyl cycloheptene were formed but unexpected products such as benzyl cyclohexane, alkoxides products and cyclohexyl phenyl ketone were also formed. A different product distribution was observed when the polymer bound sulphonyl hydrazone were decomposed. Using polymer supported sulphonyl hydrazone of cyclohexyl phenyl ketone was not ensured advantage according to using free tosyl hydrazone of cyclohexyl phenyl ketone. XI
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