Chemical structures of compounds 1-5 were determined by comparison of their melting points and U spectra as well as other spectroscopic data with literature values.!ompounds " and #$ structure identifcation is the subject of this study.
Chemical structures of compounds 1-5 were determined by comparison of their melting points and U spectra as well as other spectroscopic data with literature values.!ompounds " and #$ structure identifcation is the subject of this study.
Chemical structures of compounds 1-5 were determined by comparison of their melting points and U spectra as well as other spectroscopic data with literature values.!ompounds " and #$ structure identifcation is the subject of this study.
Tugas : Review Jurnal Kimia Bahan Alam Aulia Vellarani (M0310010)
Flavonoid compound from Maclura Pomifera and Maclura tinctoria
Jurnal 1 : Flavonoid from Maclura tinctoria From the first journal we explaining about the main structure of flavonoid . The chemical structures of compounds 1-5 were determined by comparison of their melting points and U spectra as well as other spectroscopic data with literature values. !ompounds " and #$ structure identifcation is the subject of this study. The F%&'( of " suggesting the molecular formula !)1*))+11. The U spectrum showed a major absorbance at )," nm characteristic of a flavanone s-eleton. % singlet at d 1).1.$ which disappeared on deuterium exchange$ indicated a !-5 hydroxyl.The proton at !-) appeared as a double doublet at d 5.". /0 1 12 and 2 *34. The e5uatorial proton of !-2 appeared at d ).". as a double doublet. 6n the 12! 7'8 spectrum$ the signals for !-) and !-2 appeared at d #..) and .1.5$ respectively. % two-proton signal at d 5.,, appearing as a singlet was assigned to *-" and *-,. % two-proton signal at d ".5" appearing as a multiplet was assigned to *-29 and *-59 and a one-proton signal at d #.2 was assigned to *-"9. These 1* 7'8 data indicated that the % ring was hydroxylated at positions 5 and #$ while the & ring at )9 and .9. The 12! 7'8 data further established the hydroxylation at !-)9 since the chemical shift of !-) resonated at d #..1 indicative of the presence of a )9- oxysubstituent. 1* 7'8 resonances at d 2.5:2.) and six signals in the 12! 7'8 spectrum at 1;;.<:"1." indicated the presence of an +-sugar moiety. % loss of 1") mass units from the molecular ion in the F%&'( and a signal at d "1."$ represent a !*) group suggested a hexose moiety. The anomeric glucose proton appeared at d .., as a doublet with a coupling constant for *-1;=*-); of 0 1 #.5 *3$ indicating a b-lin-age of the glucose unit to the aglycone. The above data with the 12! 7'8 spectrum />?@T se5uence4 were found to be consistent with a flavanone glucoside structure. The glucose unit was placed on the !-.9 position based on the value of the proton of the anomeric carbon /d ..,4 and the *'&! correlation observed between the anomeric proton of glucose and carbon .9. Thus$ " was assigned as 5$#$) 9-trihydroxyflavanone.9-+-b->-glucoside. !ompound #$ was named !)2*).+11. %n isoflavone s-eleton was suggested by U absorbance at )5< nm in the proton 1* 7'8 spectrum of a one proton singlet at d ,.)). The U value of band 66 /ring %4 at d )5< nm was about " nm nearer in the U than the e5uivalent 5-hydroxyisoflavone glycoside /1a4. The 12!7'8 spectrum provided additional conformation of the lac- of a free 5-+* group as the carbonyl signal of # resonated at d 1#5.1 instead of 1,;.; as shown in the spectrum of compound 1a. The #-hydroxyl group was free as indicated by a bathochromic shift in band 66 /ring %4 of 11 nm upon the addition of sodium acetate. The 1* 7'8 spectrum showed a one proton singlet at d "... indicating that ring % was trisubstituted. From *'&! data this proton showed correlations with carbons 5 and , instead of " and <$ therefore it was assigned to position ". 8ing & showed a pattern of three one-proton signals at d #.;,$ d ".## and d ".<1$ the mutiplicity of which showed not coupled to each other. The si3e of the coupling constants /1.# and ,.) *34 is characteristic of meta and ortho couplings as found in a 29$. 9-oxygenated flavonoids. The presence of two methoxyl groups in the molecule was indicated by a pea- in the 1* 7'8 spectrum at d 2.#< appearing as a singlet and integrating for " protons and from long-range !+(A connectivities the positions of the methoxyl group on ring % and ring & were conformed since cross-pea-s from *-" to +'e were found as well as from *- )9 to +'e. The 12! 7'8 spectrum showed signals at d #2."$ #1.)$ #<.1$ #;.<$ ,1.< and "1." characteristic of a !-glucoside. The glucose residue was assigned to position , based on *'&! correlations. The conformation of the anomeric proton was deduced to be b based on the signal at d ..# appearing as a doublet with a coupling constant of <.5 *3. The structure of # was thus established as orobol 5$29-di-+-methyl-,-!-glucoside. Jurnal 2 : Development of sorbents for immunoaffinity extraction of isoflavonoids >espite the high number of isoflavonoid compounds and the different degrees of their complexity$ it is reasonable to expect that the simplest isoflavones /e.g. daid3ein and genistein4 should be present in all isoflavonoid-producing species as the precursors of the more complex ones. Their detection thus may be used as an indicator of the presence of the isoflavonoid metabolic branch in the newly studied taxa. This reasoning led us to develop an off-line combination of immunoaffinity chromatography /6%!4 and *@B!C?(6-'( for the detection of simple isoflavones in plant extracts. >etection of these secondary metabolites in non-legumes is impeded by the complex matrix of plant material and low concentration of the analytes. 6n this study$ we present Tugas : Review Jurnal Kimia Bahan Alam Aulia Vellarani (M0310010) a combination of immunoaffinity chromatography /6%!4 and *@B!C?(6-'( as a new tool for the detection of isoflavonoids. 6ni adalah ligan-ligan -onjugat yang diguna-an sebagai imunogen untu- mensintesis senyawa isoflavonoid dimana stru-tur dasar dari imunogen tersebut sudah mengandung gugus isoflavon. 7ama dari senyawa ligan tersebut adalah anti-#-+-carboxymethyl-daid3ein /%4 dan anti-.D;-+-carboxymethyl-genistein /&4. There was a high number of interfering pea-s and an uneven baseline on the chromatogram of the crude extract$ even with the analysis in the (6' mode limited just to four selected ions. results of the application of two different genistein-specific immunosorbentsE /14 genistein-# 6($ which has high affinity towards genistinF /)4 genistein-.; 6($ which has high affinity towards sophoricoside and to daid3ein. The detection of genistein was more or less expectable in '. pomifera$ as genistein is li-ely to be a metabolic precursor of osajin and pomiferin$ the well -nown isoflavones associated with this plant species. 'oreover$ several other simple isoflavonoids were detected for the first time in '. pomifera and Ficus carica by means of the off-line combination of 6%! and *@B!C?(6-'(. Ge conclude that the prepared set of immunosorbents can be used in combination with *@B!C?(6-'( as a valuable tool for sensitive detection of simple isoflavonoids as indicators of thepresence of the isoflavonoid metabolic pathway in non-leguminous plants. Tugas : Review Jurnal Kimia Bahan Alam Aulia Vellarani (M0310010) Senyaa Flavonoid dari Maclura pomifera dan Maclura tinctoria Jurnal 1 : Development of sorbents for immunoaffinity extraction of isoflavonoids >alam suatu bahan alam banya- se-ali ditemu-an jenis senyawa isoflavonoid dan ting-at -omple-sitas mere-a yang berbeda$ oleh -arena itu dimung-in-an bahwa senyawa isoflavon sederhana /misalnya daid3ein dan genistein4 dapat ditemu-an di semua jenis tanaman penghasil isoflavonoid sebagai pre-ursor yang lebih -omple-s. Heberadaan mere-a dapat diguna-an sebagai indi-ator adanya cabang metaboli- isoflavonoid dalam penelitian ta-sa baru. %lasan ini mendorong adanya pengembangan -ombinasi -romatografi immunoaffinity /6%!4 dan *@B!-?(6-'( untu- mendete-si isoflavon sederhana dari e-stra- tumbuh-tumbuhan. >ete-si metabolit se-under tanaman non polong terhambat oleh matri-s -omple-s bahan tanaman dan -onsentrasi rendah dari analit. >alam penelitian ini$ diguna-an -ombinasi -romatografi immunoaffinity /6%!4 dan *@B!- ?(6-'( sebagai alat baru untu- mendete-si isoflavonoid. 6ni adalah ligan-ligan -onjugat yang diguna-an sebagai imunogen untu- mensintesis senyawa isoflavonoid dimana stru-tur dasar dari imunogen tersebut sudah mengandung gugus isoflavon. 7ama dari senyawa ligan tersebut adalah anti-#-+-carboxymethyl-daid3ein /%4 dan anti-.D;-+-carboxymethyl-genistein /&4. a. b. >an beri-ut adalah beberapa senyawa isoflavon sederhana yang diidentifi-asi dengan 6%! dan *@B!- ?(6-'( E (edang-an beri-ut adalah senyawa isoflavon yang teridentifi-asi memili-i gugus gabungan isoprene atau terpenoid E a. +sajin b.@omiferin
>ari -romatogram dalam jurnal$ada beberapa punca- yang menyimpang dan dasar yang tida- merata pada -romatogram dari e-stra- -asar$ bah-an dengan analisis dalam modus (6' terbatas hanya untu- empat ion yang dipilih. *asil dari penerapan dua immunosorbents genistein-spesifi- yang berbedaE /14 genistein-# 6($ yang memili-i afinitas tinggi terhadap genistin$ /)4 genistein-.; 6($ yang memili-i afinitas tinggi terhadap sophoricoside dan daid3ein. >ari hasil menunju--an senyawa genistein lebih bisa diharap-an dijumpai dalam '. pomifera$ seperti genistein yang menjadi pre-ursor metaboli- osajin dan pomiferin$ isoflavon yang sangat sering dijumpai dalam 'aclura. Hami menyimpul-an bahwa penggunaan immunosorbents dapat diguna-an dalam -ombinasi dengan *@B!-?(6-'( sebagai alat untu- mendete-si adanya senyawa isoflavonoid sederhana sebagai indi-ator adanya jalur metabolisme isoflavonoid pada tanaman '. pomifera. Jurnal 2 : Flavonoid from Maclura tinctoria (tru-tur -imia senyawa 1-5 ditentu-an dengan perbandingan titi- leleh dan spe-trum U serta data spe-tros-opi lainnya dengan literatur. (enyawa " dan #$ adalah sutru-tur yang dibahas pada jurnal ini. &erdasar-an F%&'( menunju--an rumus mole-ul dari senyawa " adalah !)1*))+11. (pe-trum U O N H O + &(% 8 + + * gugus isoflavon O H N O + &(% +* + gugus isoflavon *+ O OH * + daid3ein *+ O OH +* + genistein *+ O OCH 3 * + biochanin *+ O OH * + isoformononetin !* 2 + O OCH 3 * + formononetin *+ O OH +* + prunetin !* 2 + O OH * + daid3iin Ilu + O OH +* + genistin Ilu + O OGlu +* + sophoricosida * + O OCH 3 +* + sissotrin Ilu + O OCH3 * + ononin Ilu + O O + +* +* * isoflavon isoprene Terpenoid O O + +* +* +* isoflavon isoprene Terpenoid Tugas : Review Jurnal Kimia Bahan Alam Aulia Vellarani (M0310010) menunju--an absorbansi besar di )," nm identi- dengan gugus flavanone. (ebuah singlet di d 1).1.$ menunju--an proton hydroxyl !-5. @ada !-) muncul sebagai doublet ganda pada d 5$". /0 1 12 dan 2 *34. @roton !-2 muncul di d ).". sebagai doublet ganda. (ebuah sinyal dua proton pada d 5$,, muncul sebagai singlet menunju--an gugus *-" dan *-,. (ebuah sinyal dua proton pada d ".5" muncul sebagai multiplet menunju--an gugus *-2 9dan *-59 dan sinyal satu-proton di d #.2 menunju--an gugus *-" 9. >ata 1*7'8 menunju--an bahwa cincin % adalah hidro-silasi pada posisi 5 dan #$ sedang-an cincin & pada ) 9dan .9. >ata 7'8 12! selanjutnya menunju--an hidro-silasi pada !-)9 -arena pergeseran -imia dari !-) di d #.$1 mengindi-asi adanya )9-oxysubstituent. 8esonansi 1* 7'8 pada d 2$5 : 2$) dan enam sinyal dalam spe-trum 7'8 12! pada 1;;$< : "1$" mengindi-asi-an adanya gugus +-Ilu. @roton anomeri- glu-osa muncul di d .$, sebagai doublet dengan -opling -onstan untu- *-1;=*-); 0 1 #$5 *3$ menunju--an hubungan dari unit glu-osa menjadi agli-on. Unit glu-osa ditempat-an pada posisi ) 9 berdasar-an nilai dari proton dari -arbon anomeri- /d ..,4 dan -orelasi *'&! diamati antara proton anomeri- glu-osa dan -arbon .9 !-.. >engan demi-ian$ " disebut sebagai 5$#$) 9-trihydroxyflavanone .9-+&>-glucoside. (enyawa #$ bernama !)2*).+11. (ebuah -erang-a isoflavon ditunju-an oleh absorbansi U pada )5< nm. 7ilai U band 66 /cincin %4 di d )5< nm adalah se-itar " nm de-at dalam U daripada setara gli-osida 5- hydroxyisoflavone /1a4. The 12!7'8 spe-trum yang tersedia -onformasi tambahan dari tida- adanya gugus 5- +* bebas sebagai sinyal -arbonil dari # bergaung di d 1#5$1 1,;$; bu-annya seperti yang ditunju--an dalam spe-trum 1a majemu-. The (pe-trum 1* 7'8 menunju--an proton singlet di d "... menunju--an bahwa cincin % tersubstitusi. >ari data yang *'&! proton ini menunju--an -orelasi dengan -arbon 5 dan , bu-an " dan <$ -arena itu ditugas-an -e posisi ". !incin & menunju--an pola tiga sinyal proton di d #.;,$ d ".## dan ".<1 d$ mutiplicity menunju--an tida- berde-atan satu sama lain. U-uran dari -onstanta -opling /1$# dan ,$) *34 adalah -ara-teristi- dari meta dan orto -opling seperti yang ditemu-an di 2 9$ .9 flavonoid-o-sida. %danya dua gugus methoxyl dalam mole-ul ditandai dengan punca-nya pada 1* spe-trum 7'8 pada d 2$#< muncul sebagai singlet dan mengintegrasi-an untu- " proton dan dari -one-tivitas !osy jang-a panjang posisi gugus methoxyl pada cincin % dan cincin & yang sesuai seja- lintas punca- dari *-" sampai +'e ditemu-an serta dari *-) 9untu- +'e. (pe-trum 12! 7'8 menunju--an sinyal pada d #2$"$ #1$)$ #<$1$ #;$<$ ,1$< dan "1$" -ara-teristi- !-glucoside. 8esidu glu-osa berada posisi , berdasar-an -orelasi *'&!. Honformasi dari proton anomeri- itu disimpul-an menjadi b berdasar-an sinyal pada d ..# muncul sebagai doublet dengan -onstanta -opling <$5 *3. 'a-a stru-tur # disebut sebagai orobol 5$2 9-di-+-metil-,-!-glucoside. &eri-ut adalah stru-tur flavonoid yang telah banya- diidentifi-asi pada tanaman 'aclura E 1 ) 2 . 5 &eri-ut adalah stru-tur flavonoid baru yang teridentifi-asi pada 'aclura tinctoria E " #
O + +* +* +Ilu +* steppogenin .9-+-b->- glucoside O + +* +* +* +* +* 2$5$#$)9$. 9-pentahydroxyflavanonol O +'e +* + +'e +* Ilu orobol 5$29-di-+-methyl-,-!-glucoside O +* +* + +* +* * 5$#$29$. 9-tetrahydroxyisoflavone O + +* +* +* * +* 2$5$#$.9-tetrahydroxyflavanonol O + +* +* +* +* 5$#$)9$. 9-tetrahydroxyflavanone O +* +* + +* Ilu + * orobol #-+-b->-glucoside