SINTESIS SENYAWA - SENYAWA ANTARA VINILOG KURKUMINOID
ABSTRAK
Sintesis senyawa-senyawa antara atau antara vinilog KurKuminoid secara relay-point Melalui transformasi dan degradasi gugus fungsi telah dilakuKan dengan menggunaKan bahan baku piperin. Piperin se -Legal baton baku berhasil diisolasi dari buah matang lada hitam (Piper nigrimn L) dengan perolehan 4, 1 % terhadap berat kering buah matang lada hitam. Senyawa-senyawa antara vinilog KurKumninoid yang berhasi1 disintesis adalah: Asam piperat yang diperoleh melalui hidrolisis piperin dengan menggunakan 10% KCEi alKoholis, dan basil percobaan memberikan perolehan 97,8% terhadap piperin murni. dietil piperoil malonat berhasil disintesis dengan mereaksiKan piperoil Klorida dengan dietil magnesium malonat pada suasana basa dengan perolehan 40, 13% terhadap piperoil Kiorid. Piperoil Klorid adalah Klorid asam yang dibuat dari asam piperat dengan tionil Klorid. Etil piperoil asetat diharapkan dapat diperoleh dengan me1akukan hidrolisis parsial pada suasana basa atau asam terhadap diester dietil piperoil malonat. Penelaahan struKtur senyawa-senyawa basil sintesis dilaKukan
dengan speKtrosKopi ultra lembayung, inframerah,resonansi magnet anti 1HrMR
dan
13Cj,
speitrosKopi massa dan analisis elemental.
Senyawa-senyawa basil sintesis dapat dibedakan dari senyawa asalnya melalui serapan maxsinum pada panjang gelombang dari senyawa senyawa tersebut, frekwensi vibrasi KaraKteristiR gugus Karbon pada
viii
spektrum inframerah, dan puncak ion noleIul (Mt') dari senyawa-senyawa tersebut. Piperin (T1.130,0-130,5 °C) memberikan ).X 341,20 nm ( log 6=4,82), Amax 311,80 nm (log 6=4,60), dan
VC=O
pada 1635 cm
-1
untuk vibrasi regang C=0 amid. Asam piperat (T1.216-218 °C) dengan l a x 340,20 an (log 6=4,40), 310,60 nm (log 6=4,20), untuK
1686 cm-
VC=O
vibrasi regang C=0 asam Karboksi l at, m/z 218 (M+) dan
rg/z
l
173
(int.rel 100%), analisis elemental mempunyai probabilitas Kesesuaian 99,8% dan hasil analisis adalah 66,05% C, 4, 627. H dan 29,33% O. Die til piperoilmalonat (T1.91-92 °C) memberikan Amax 376 nm (log 6= 4, 60)
VC_O
1705 cm-4 untuk vibrasi regang C=O ester, dan puncak
ion molekul ln/z 358 (M+), m/z 200 (int.rel 100%). Senyawa basil bidro-Isis parsial diester dietil piperoilmalonat dalam suasana basa memberikan Amax 336, 80 nm (log 6=5, 60) , vC=O 1660 cm-1 adalah vibrasi regang untuk C=0 asam, puncak ion molekul dan
nyz173
(int.rel
1007.),
puncak-puncak
rryz
1HNMR
218 (M+)
memberikan
pergeseran Kimia 6 5, 89;
d
5, 94;
6
6, 01;
d 6, 77; 6
6, 93;
d 7,
34; 6 7, 71 ; Puncak-
puncak 3C[U
R n;emberiKan pergeseran Kimia
105,36 ;
6
6 144,14;
108,46; 6 120,81; 6
147,83;
6
6
d
122,21;
39, 60; 6 77, 64; 6
6
100, 94; 6
124,21;6 130,00; 6 139,25 ;
148,01. Hasil hidrolisis parsial ini KemungKi-
nan bukanlah senyawa yang diharap an yaitu ester etii piperoilasetat n 1ainKan Kenungkinan kembali Ke asannya yaltu asam piperat.
ABSTRACT
The synthesis of curcuminoid vinylogue intermediates through the transformation and degradation of functional groups was done by using piperine as the starting material which acted as the relay point of the synthetic plan proposed. Piperine as a starting material was isolated from the dried ripe fruit of Piper nigrzun L., Piperaceae (black pepper). The piperine content of the fruit was 4.1 %. The curcuminoid vini1ogue intermediates which were synthesized in this respect are: Piperic acid which was acquired through the hydrolysis of piperine using 10% ethanolic KGii with a 97.8% yield. Piperoyl diethyl malonate, as a result of the reaction between piperoyl chloride and the organomagnesium of ethyl malonate with a yield of 40.13'%. Piperoi1 chloride as the acyl chloride of its carboxylate, piperic acid, was acquired through the action of thionyl chloride to the carboxylate. Ethyl piperoil acetate was targeted as a result of a partial basic or acidic hydrolysis of the diethyl piperoil malonate. Structure elucidation of the synthesized compounds through spec troscopic determinations, UV, IR, 111NMR and
13cNm,
NS, and also ele
mental analysis, concluded that the compounds in respect could be differentiated from its parent compounds. x
X1
The data acquiured for the parent molecule and their synthesized derivatives are as follows: Piperine (rip 130.0-130.5 °C) with
X
341,20 rm (log 6=4,82), 311, 80 rm (log 6=4, 60), dan VC=O at 1635 cm
-1
for C=O amide stretching vibrations. Piperic acid (rip 216-
2180C) with
Airy
340,20 rm (log 6=4,40), 310,60 rm (log 6=4,20), VC=O
1686 cm
-1
and
173 (rel. int. 1007.), elemental analysis data having a 99,8%
nyz
for C=0 stretching vibration of a carboxylate, nz/z 218 (M+)
probability factor showed 66, 05% C, 4, 627. H dan 29, 337. O. Diester diethyl piperoyl malonate (mp 91-920C) rnemberikan Amax 376 un (log 6= 4,60), VC=O 1705 cm-1 for C=0 vibration and ester, and molecular ion peak
nyz
358 (M+),
n;/z
200 (rel. int. 100%). The compound re-
sulted from the basic partial hydrolisis of the diester diethyl piperoil malonat gave Amax 336, 80 rm (log 6=5, 60),
VC=0
1660 cm-1 is stret
ching vibration for C=0 of an acid. Molecular ion peak of
14/z
218 (M+)
and rn/z 173 (rel. int. 1007.), chemical shifts of its lHNMR analysis gave 65, 89; 6 5, 94; 6 6, 01; 6 6, 77; 6 6, 93;
6
7, 34; 6
7, 71 .
Its
13CNMR
spectra showed chemical shifts at 6 39,60; 6 77,64;
100, 94; 6 105,36; 6
139, 25;
6
6
108, 46; 6 120,81; 6 122, 21; 6 124, 21;
144, 14; 6 147, 83;
6
6
6
130, 00;
148,01 . The result of the partial
hydrolysis could be concluded as most probably is not piperoiyl acetat as expected but piperic acid.
