ri
XIX INTERI{ATIONAL CHEMISTRY SEMINAR
Pal $il
Yoryakart&, eo May zoog
Jointll'held br':
Department of Chemistry
Facultl' of N{athernatics and Natural Sciences
LTnir-ersitas Gadj air
X'i
ada
and
Indonesian Chemical Sociefy"
Branch of Yog'akarta Special Region
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ISSN NO- 1410-8313
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CONTENT
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.............
REMARK OF HEAD OF GHEMISTRY DEPARTMENT
iii
REMARKFROMTHE ORGANIZING COIi}'ITTEE
BEMABK FROM DEAN OF FACULTy AF MATHEMAnCSATUD
V
NATUBAL
vi
SGIENCES
REIilARK
FM
THE
BB TON OF UHIVERSilTAS GA[L'A}I
T'4D4..,.....
Vii
CONTENT
PAPER GRUOP
ORGANIC CHEiIISTRT GEOUP
1.
ZnBrd?€lumina ad HW-alumina : an lmprp!rcd cdalyst for the highly
selecfive syntheeis ol menthols starting lrom (+)rcitonellal in two-step
process
1
Elvina D. lftitah, M. Muchalal, WegaTrisunaryanti, Ria Armunanto
Z
Erlrymatlc lletilanolysls of Palm OII Uslng Rlce Bran as Llpase
Ptdfi ltastuti, R*w ldati, Tqwin Yuliyanto
3. ilw
tiothod tor the S$hesis ol
Rrtmabni, Varinder K. Aggarwal
Source.....
llexahydropyidazine.
4.
Synthesi s 3, 4-Di methoxybenzyl -2,4-Di h ydroxyphenyl Ketone From
Eugenol
Sabiin MabW, Attdt Haifil Alimt#in, Mdasir, Eti Narwenirg Sholikhah
5,
Phospholipid r{cs prent at pumpkin sed kernels oil (&rcurbita
moschata (Duch) Poir)..........
Laily Nurliana, TriJoRo Raharjo, Sabirin Mastjeh
6
11
18
6, The use of lignin trun
pulp blacle liquor with palm emfi bunch
malsiats in the prooss oI slow rebas urm tabbt fertilizer
Lucy Arianie,
7.
Ahrd
24
Mulyadi, Atghani Jayuska
Santhesis and Gharacterization of Nonionic $rrtactant of Alkanolamide
Derivatives from Castor Oil (Ricinus
communis)................
30
M. ldham. D. M, Musih Anwar, Aditia Diyah, Teguh Apiyanto, Miftah faried
and Tutik Dwi Wahyuningsih
8.
Synthesis and Activity Test as lleoryrlbose
AsymrHric
@rdation
Dibsaletones.............
lnhibltor of Two
.
35
Sd llandayani, Sabirin Matsieh, Chahil Anwar, Sri Atun
vlu
rssN No. 1410-8313
lntornational 8[smistrl Ssminrr Pr0000tiliu
Ibgruftirra 26
i'.{er'
ilN&
SYNTHESIS AND ACTIVITY TEST AS DEOXYRIBOSE DEGRADATION
INHIBITOR OF TWO ASYMMETRIC DIBENZALACETONES
Sri Handayani''., sabirin Matsjeh2, Chairil Anwaf , SriAtun'
lDepartment of Chemical Education, Faculty of Mathematics and Natural Sciences,
State University of Yogyakarta, Karangmalang, Depok, Yogyakarta 55281, lndonesia
2Chemistry Departement, Faculty of Mathematic and Natural Science
Gadjah Mada University, Bulaksumur, Yogyakarta, lndonesia
" Co*veffimtdfrlTrg
ffiaffiw,r,,
Mt:rihx:
Wi!ffi&?ffi2"
e,rnaff:
ABSTRACT
Synfhesis and activity fesf as deoxyribose degradation inhibitor of tuvo asymmetric
dibenzalacetones have been conducted. The first compound, 1(E),4(E)-1-(4'methoxyphenyl)-5-phenyl-1,4-pentadiene-3-one was synthesized fram benzaldehyde,
acetone and 4-methoxybenzatdehyde. The second, 1{E),4(E)-1-(3',4'-dimethoxyphenyl)-5-
phenyl-1,4-pentadiene-3-one was from benzaldehyde, acetone and 3,4dimethoxybenzaldehyde. Those compounds were synthesized by crossed aldol
condensation in base condition with water-ethanol solvent. The synthesize of both
compounds using ice bath throughout the stirring. The precipita.te was purified by coloumn
chromatography. Each product was characteized by FTIR, 'H'NMR, "C-NMR, HMQC
and HMBC. Activity tesf as deoxyribose degradation inhibitor showed lCso of both
compounds are 1,7pM and 1,02 yM respectively.
Keyword s :
a
sy m m etri c d i b e n z al a ceton e,
d
e oxy
INTRODUCTION
Aldol Condensation has been
occurred by a nucleophilic addition of
enolate ion to a carbonyl group. Acetone
also undergoes aldol condensation, but
the equilibrium concentration of the
product was generally small. Cross aldol
condensation between pannisaldehyde
ribose degrad ati o n
in
followed by
hi
bitor
reaction
with
and Arty
have
cynnamaldehyde [3].
Handayani
synthesized 1(E),4{E)-1-5diphenyl-1,4pentadiene-3-one and its derivatives were
known as symmetrical dibenzalacetone
that have been made by crossed aldol
condensation between acetone:benzaldehyde (1:2). lt also tested as a radical
Asymmetric
from fennel oil with acetophenone hydroryl scavenger t4l.
produced 2{rydrory4angftoryc*ralcone crossed aldol mndensation have been
compound [1]. The influence of base done with various eatalyst [5,6,7]. Tutik D
has synthesized of symmetrical
concentration and reaction time on the
cross aldol condensation reaction has dibenzalacetone which have similar
skucture with the cinnamic acid derivative
also been reported t21. AJnustone or
4(E),6{E)-1,7diphenyl-4,6*reptadiene-} I8l. Fronr its structure, it could be
one is an asymmetric mmpound *tat estimated t'rat benzalacetone and
isolated ftom Curcuma xanthonhiza dibenzalacetone, which have similar
(Zingiberaceae). This compound was structure with cinnamic acid or its
synthesized by Goksu, et al. using derivative, have ultraviolet absorption in
crossed aldol condensation between the same range. Thus, asymmetric
benzaldehyde and acetone, wtrich then dibenzalaretane was esfimated as a
radical scavenger and also a sun screen.
Htndayani et al.
35
htffnatioml 8[smi$try Sonimr
"lilg.:d;:ttr:ta
Prooooding
}ll'i'li*t I{tf}*
ln this research two of
asymmetric
dibenzalacetones, compounds 5 and 6
namely 1(E),4(E)-1 -(4'-methoxyphenyt)5-phenyl-1,4-penladiene-3-one and
1 {E},4(E}-1 -{3',4'dimethoxyphenyt}-5.
phenyl-l,4.pentadiene.3-one
will
be
4-methoxybenzaldehyde in order to
synthesize compound 6 (Figure '1). Four
fractions obtained from
chromatography, and
the
the
column
target
compound was identi:lied using thin layer
chromatography with chloroform-hexane
synthesized.
4:6.
EXPERIMENTAL SECTION
Materials
Deoxyribose assay.
The assay was performed follow the
method as described hy Ftaltiwetl [9] Att
soluticns ,uws fre*d,V exwrcC. lroto *
solutlo* CIf S.? ilr$ 6 rffi# Zdeoxyribose
was added 0.2 ml ascorbic acid 0.01 mM;
0.2 ml buffer phosphate (pH 7.4);0.2 mt
0.01 mM HzOz, 0.02 ml of various
concentration sample {0,24; 0,48; 0,95;
'1,89; 3,78 plM) and 0.2 ml ferrosulphate
0"1 mM. After an incubation period of 30
minutes at 3100K, the extent of
deoxyribose degradation was measured
by the TBA reaction. 3 ml of TBA and 3 ml
All materids used frnm. Merck
.Sd4rffi
ffi{fiH,
rnethor#mis#dd1@,
3.4-
afi?eftg
dimethoxybenzaldehyde,
chloroform
ethanol, benzaldehyde, hexane, and ethyl
acetate. TLC was carried out using 0.25-
mm plate Silica gel Merck 6A
F254,
column chrornatography were perfonned
by Silica get60 {230400 mesh)"
lnstrumentation
The]H, ,.C.NMR, HMQC and HMBC
Spectra were recorded on 500 MHz Jeol
spectrophotometer. lR spectra were
conducted using a Shimadzu 8300 FTIR
spectrometer.
Procedure
Synthesis of compounds 5.
lnto a solution of NaOH @.A25 mol,
19) in aqueous ethanol {1:1) trat was
prepared at ambient temperature, 1
benzaldehyde (0.01 mot, 1,06 g),2 acetone
(0,01 mol, 0,58 g) and 3
4-
methoxybenzaldehyde (0,01 mol, 1,66 g)
were added drop wise altemately. Afier
additional stining for 60 minutes, water (20
ml) was added to tfre reaction mixture
which then filtered. The extract was washed
with water (20 ml x 3) and separated by
column chromatography (d 2.5 cm, h S0
cm), with silica gel 60 (230400 mesh) as
the stationary phase and ethytaetate-
hexane 1 : I as the eluent. The target
compound (5) was identified using thin
layer chromatography with ethylacetatehexane 5:1 as the mobile phase.
Synthesis of compound 5.
The similar procedure was repeated
for 3,4-dimethorybenzaldehyde to replace
Ilandayani el aL
of
TCA were added
to the reaction
mixture and heated for 15 minutes at
3530K. After the mixture being cooied, it is
read at absorbance 532 nm against a
blank (the same solution but without
sample). The percentage inhibition was
calculated by the formula:
4..
_A
"hlauh ":utPtL
I ('/o) =
.f l
00%
4,,t.,n,.
The lCsr value represented the
of the compounds that
concentration
caused 50% inhibition. BHT was used as
a posrtive control.
RESULTS AND DISCUSSION
lmproved Synthesis of Compound 5
Separation of the product of
crossed aldol condensation between
benzaldehyde, acetone and 4-
methoxybenzaldehyde was done by
coloumn chromatography. The product
from coloumn chromatography separation
yielded 3 fractions, which were identified
by TLC with hexane-ethylacetate S:1 as
the eluent. Retardation factor datas from
TLC scanner showed that fraction ll was
the target of
compound
5
(10,6%)
determined as yellow residue. Fraction
I
36
hlff!r$$$
c.lrEfi$ry 8!Emr
lrellllbg
rsstY$o. r4t&83r3
fuw,&,ww.3{)3fu1 .M6B
to
and fracton tl
be
supposed
benzala*et*ne and diamisaia**tcne a$ the
produoi$
sr&$sed aldal
condensation reactionChame,terization of comp*und 5 hy
F?tR {KBri resultad peaks qn 3S35; 2823;
2ffr2: 1888 1423:1445: and 1775 srt1.
A series cf *vre and &va dirnensio*al f*fifrfi
S {Figure 1}. The yiel$ of crossed atdol
*onde*sation betw*en acctsne, 3,4-
spectro*c*si* experlr**r* using I-{MGC
as pale yaltcw oil.
of
side
and Hetersnl,clear Multiti$e
Coherence {HMBC} pattems wsre
perfonned to a*sign the praton and
carbon res*nafice welation cf the
mmpounds. The signal pattem sf the
dimetlrexybenzaldehyde
eompounds. There uras $eparated by
G*lurnn Chr*rnat*graphy {Ac$ft-hexane,
t:9| to provide ihe asymmetric
diknEalacetoile t i15,53Dlo) determined
The rnu{tip{e bcnd wnelation sf
Bond
arornatic *ng showed th* in{lu+nce *f
rnetlrcxy {#&Ae} in S 3,8 {3}t, s} ppnt
(Figure 1;'f able'll-
o"
o
I
,\
-A)
J.
C
I Scfier*e sf cross aldd condensation fo
synthesieed of compound 5 and S.
Fig,
Table 1. IH, 13C-NMR and ttMBC dates of
oompourd 5 {CDQs}
psr_ _
(5HlMHz)
143 C6", C2,C3
I
7,7A {tH; <t}
tf,,3,4 Ci}, CZ
2
6,97 {1H; d}
3-188
I
125,7 C3, Cl"
7,aT (tH;dl
143,3
tP
t1{,6
56
162
1m,3
r?7,8
128.5
,&u1*
j3!,5
C3
C{, G3', 04'
Ol['
(}t"
C5, C6"
04', C2'
C1".
ur.v
C5,
Cr
Cf
frrBrored,$ymf&esis *f **mpourd S.
The preparaiion of compouno B was
initiated by the mixing af 1.2 and 4 to giqe
ef aI.
im*thcxyphenyl)-5-phenyl- 1,4-
Tabl* 2. tH, '*c-h,MR and IIMBC datas of
compound 6.lCQS'e) _ ,
--
6
Ilanilalani
1;
Table ?). ln the IH-NMR spectrum (500
&{Hz, C*Slrl, M pattem$.einglet, nine
d*ublet and three double dublet were
sbserurd. The double dublet at D = 7,2;
?,S1;*r'ld 7,41 was assign€hle to H2", H3"
and H5" respectively. Two equivalenee
methcry signals at 6 3,gl and 3,9 were
asslgncd to C3' and e4'. $uppoil spectra
data prcvided by the tR {KBr}, which
indicaies the existence of C=O {1645cm1),
aromatic C=C (1514-1417 cm-l) and
CO etir*r {1255-113$ rm-l}. Therefore,
the structurc of G was 1{E},4{EF1-(3',4'pe*t*di*ne-3-on*.
.\-'o.t"r
7;t1(1H; d)
5
7.58 {fi; d}
3'n5o S,93 {2H; d)
",6'
4'-OMe 3,8; (3H, s)
4',
7,61 (1H; d)
X
3",5' 7,'l {2H; d)
q'
t
7,a,
tr*r1rr1ru,
tlH; d)
7,62 (2H;C)
6"
HMBC supported the structure (Figure
d
$["\
and
benzaldehyde tuas a mixture cqnsist of 4
no.
6l-t
{IH; mi
pgm
SC
pPm
HMBC
-
124
c3
2
6,94 {1H; d}
3-180
1?5,8 c& cf
1
vio $H: dl
Cg
143
7,?4 flH;d)
5
C3
?,6{1}l;d} 110
t
161
3'
"
C4'
S
3'{Irie &9 {3tl; s)
4',-15a
C3'
#-gt{e &91(3H;s} 56
111 O4', C8', Cl'
t,83 {1H; d}
S'
120 C1', C5', C4'
S,89 {1H; d)
6'
c5
r
7,6111H;#l 1*
?3 (1H; tldl
1zl.it G1'. et'
f
C3"
7,14 {1H; d}
1'10
'*'
tz$
C1'
7,33{11{; d)
5"
Seoxyribosa assay
A*W& t*sl eS
d*oxyribcs*
degraclauon innrottor^was oon6, by fentot,
reactir:n
i9l The iClr vatue fepresente#
tfr* c*nffintrctisn nf the csmpounds. that
cgrsed 5*% inhibfir"on. -+il ex$rir{rent
I $rere canied out 6in
triplicate{.
3?
Determination of
in Table 3.
lCso values
showed
were
9. Halliwell, B.,Gutteridge, M.C., and
Auroma, O.1., 1987, Analytical Bioch',
165,215-219.
1,7
1,02
CONCLUSION
ln conclusion, two asymmetric
dibenzalacetones exhibited significant
deoxyribose degradation inhibitor activity.
The |CSO of mmpund 5 and 6 are 1,7 and
1,02 pM respectively. Compound 6 is
more potent than 5 to inhibit deoxyribose
degradation.
REFERENCES
1.
Handayani,
S., Sintesis
metoksiflavanon Menggunakan
4'G'
hidroksiasetofenon dan p-anisaldehida
dari minyak Adas, Master's
Thesis,
Gadjah Mada University, 2000.
S.,
Sunarto and
Kristianingrufi], S., lndonesian Joumal
of Chemissy, 5, No.2 (2005), pp 88-93"
2. Handayani,
3. Goksu, S., Celik, H- and Secen,
H-,
Turk. J. Chem.27 (2003), pp 31-34.
4. Handayani, S. and Arty, 1.S., 2008,
Joumal of Physical Science, 19{2),6168.
5. Yamano, Y., Fujitia, Y., Mizugucfti, Y.,
Nakagawa, K-, Okano, T., lto, M. And
Wada, A., Chem. Pharm. Bull., 55(9)
(2A07), pp 1365-1370.
6. Mlynarski, J., 2006, European Journal
of Organic Chemistry, 21,47794786.
7. M.Manuel B. Marques, Asymmetric
Cross-Aldol Reaction of Aldehides : A
Formidable Synthetic Chalengge,
Requimte-FGT-New University of
Lisbon (2005).
8. Tutik, D., Oksidasi Anetol dan Kajian
Pengaruh Gugus Metoksi Turunan
benzaldehide Terhadap
Reaksi
Kondensasi Benzoin dan Aldol Silang,
Master Thesis, Gadiah
Mada
University, 1996.
Handayani et al.
38