Question and Answer Final Exam

MATA KULIAH : KIMIA BAHAN ALAM
SKS : 2
DOSEN : Dr. Syamsurizal, M.Si
WAKTU : 22-29 Desember 2012
PETUNJUK : Ujian ini open book. Tapi tidak diizinkan mencontek, bilamana ditemukan, maka anda dinyatakan GAGAL. Jawaban anda diposting di bolg masing-masing.

1. Jelaskan dalam jalur biosintesis triterpenoid, identifikasilah faktor-faktor penting yang sangat menentukan dihasilkannya triterpenoid dalam kuantitas yang banyak.
2. Jelaskan dalam penentuan struktur flavonoid, kekhasan signal dan intensitas serapan dengan menggunakan spektrum IR dan NMR. Berikan dengan contoh sekurang-kurangnya dua struktur yang berbeda.
3. Dalam isolasi alkaloid, pada tahap awal dibutuhkan kondisi asam atau basa. Jelaskan dasar penggunaan reagen tersebut, dan berikan contohnya sekurang-kurangnya tiga macam alkaloid.
4. Jelaskan keterkaitan diantara biosintesis, metode isolasi dan penentuan struktur senyawa bahan alam . Berikan contohnya.

answers:
1.  Here is a terpenoid biosynthetic pathway

Picture from : (http://dc438.4shared.com/doc/vekXSryo/preview.html)

From the image above we can see that the triterpenoids derived from geranil geranil-pyrophosphate (GGPP) derived from the condensation between the units or IPP and GPP by the same mechanism. So, I think a very important factor determining the quantity produced triterpenoids which many are on the incorporation of IPP and GPP that produces farnesil pyrophosphate (FPP).

2.    Infrared spectroscopy

Spectrophotometric Infra Red or Infra Red is a method to observe the interaction of molecules with electromagnetic radiation is in the region from 0.75 to 1000 μm wavelength or wave number 13000-10 cm-1 by using a tool that Infrared Spectrophotometer.

This method is widely used in laboratory industrial analysis and research laboratories because it can provide useful information for qualitative and quantitative analysis, as well as assist in the implementation of a compound of formula-up.

IR spectra are very rich in molecular information consisting sktruktur rotational and vibrational motion.

IR spectrum lies in the range of wave numbers 12800-10 cm-1. In terms of applications and instrumentation, IR spectrum is divided into three types of radiation, namely the near IR, mid-, and far away.). IR spectroscopy to qualitative analysis methods are very useful, but difficult to do because of the similarity of each response spectrum. Quantitative analysis of the IR spectrum is also very difficult because of the overlap of the absorption spectra of the molecules in the sample. To be able to extract information from the data is complex IR spectrum, required a method kemometrik form of multivariate analysis.

NMR spectrum

Measurement of one-dimensional NMR spectra can be used to determine the structure of molecules to simpler compounds and is a known compound. Much information can be extracted from the measurement result 1 dimensional NMR spectra (1H and 13C-NMR), such as the presence of functional groups that is expressed in a typical such as the number, type and position of functional groups, the number of protons and carbon and can determine the shape conformation or spatial structure such as cis or trans, axial or equatorial.

With the known functional groups based on the measurement of 1H and 13C NMR spectra, to assemble clusters into a molecular structure is complete and correct measurements were taken two-dimensional NMR spectra. But to do intrepetasi Data 2D NMR spectral data such as HMQC, HMBC, and NOE requires considerable time given the required competence and experience Yany long enough. Besides, considering the molecular structure varies from simple to very complex.

Example:

I.                    Identification of flavonoid structure

Further analysis using IR spectrophotometer to determine the functional gugusgugus compounds are at f2 fraction is shown in Figure.

                                                    Figure of spectrum IR

Based on the figure can be seen in the pitakuat at 1714.6 cm-1 are specific to carbonyl groups. Uptake sharp 1261.4 and 1217.0 cm-1 arises from the conjugated CO group vibrations. Ribbon at 1091.6 and 1029.9 cm-1 is the absorption of the methoxy group. ribbons on 3020.3 cm-1 comes from the = CH str supported by bands between 1600 cm-1 and 1500 cm-1 indicate the presence of an aromatic nucleus. Small bands namely weak 1652.9 cm-1 derived from the group vinyl. The ribbon on the area under the 3000 cm-1 and reinforced by bands around 1450 cm-1 stated that the alkyl methylene. Based on the analysis of the spectrum in Figure , it can be concluded that the f2 containing aromatic compounds, group C = O, CO, vinyl,-CH2-and methoxy. 

I.                   Flavonoids in the leaves of breadfruit

1H NMR spectrum of compound 1 showed a signal at δH 12.85 ppm for the-OH terkelasi with the-C = O, two triplet signals of two methylene groups in the δH 3.11 and 2.97 ppm for the two methylene groups-α and -β from dihidrokalkon, and the number of signals corresponding to one unit geranil (sinyals at δH 5.17, 5.02, 3.40, 2.08, 2.06, 1.79, 166, 1.57 ppm). In addition, the analysis of signals in the aromatic region shows the unit 1,2,3,4 - substituted benzene (δH 6.71 and 6.65 ppm) and 2,4-gu-gus dihidroksibenzoil (δH 7.58, 6 , 37 and 6.35 ppm). Having regard to the value of shear proton chemical signals of two aromatic units, it was concluded that compound 1 is 2-geranil-2 ', 4', 3.4 tetrahidroksidihidrokalkon. 13C NMR data comparison between the isolated compound 1 shows the reported high compliance. It can be concluded that 2-geranil-2 ', 4',3,4-tetrahidroksidihidrokalkon defined as compounds

3. Reagents for alkaloid compounds is wagner reagents, reagent meyer, and dragendorf.

            Some of the reagents used for the deposition separated alkaloid. Reagent is often based on the ability to join metal alkaloid that has a high atomic weight such as mercury, bismuth, tungsen, or Jood. Mayer reagent containing potassium chloride and mercury jodida and Dragendorff reagent containing bismuth nitrate and mercury chloride in aqueous nitrite. Bouchardat reagents similar to Wagner's reagent and potassium jodida and Jood. Menandung silikotungstat acid reagent complex silicon dioxide and tungsten trioxide. Various reagents showed the greatest difference in alkaloid halsensitivitas against different groups. Judging from the popularity, mayer formulation is less sensitive than the reactants or dragendorff wagner.

Example:

a)      isolation of alkaloids, Most alkaloids are insoluble in petroleum ether extract but selaluu ​​should be checked for the presence of alkaloids by using one reagent precipitating alkaloids. When the number of alkaloids soluble in petroleum ether solvent, the plant material at the beginning coupled with aqueous acid to bind the alkaloid salts.

b)      Isolation of nicotine from tobacco by adding NaOH solvent

c)       Isolation of caffeine from tea leaves with sodium carbonate solvent

      4. isolation is a method to separate compounds that mix so that we can produce a pure single compound. Plants contain thousands of compounds that are categorized as primary metabolites and secondary metabolites. Usually the isolation of compounds from natural ingredients are used to isolate the secondary metabolites, as secondary metabolites can benefit human life. Among other benefits in the areas of agriculture, health and food.

            Biosynthesis is the formation of a naturally occurring molecule in the cells of other molecules that are less complicated structure, through endeorganik reaction. While the biosynthetic pathway can be defined as a sequence or a process in which consists of the stages of formation of simple compounds into complex compounds. Biosynthesis process will take place very complex, depending on the available enzymes that similar plants growing in different areas it is possible to have a certain metabolite formation paths are not identical.

      While the determination of the structure performed on the isolated compound. Determining the structure of a compound can be carried out using IR spectrum, UV, or NMR. The spectrum can identify the shape of the structure of a compound with a specific absorption.

For example; biosynthesis of flavonoids compound in Curcuma aeruginosa Roxb, then in isolation to obtain a pure single compound later identified the compound structure using IR spectrum, UV, or NMR

cholesterol

Cholesterol is a chemical compound that is naturally produced by the body which is a combination of lipid (fat) and steroid. Fat is one of the energy sources that provide the greatest calories after carbohydrate etc, but it is also one component of fat nutrients needed by the body. cholesterol must be transported to bind to proteins that form compounds called lipoproteins. One of the elements that exist in our daily diet is fat. Fat is an energy-rich substance, serves as the primary energy source for the body's metabolic processes. Fat obtained through food or formed in the body, especially the liver and can be stored in fat cells or adipose tissue for future reference. Fat cells also protects the body from the cold, and help to protect the body in many ways. Fat is an essential component of cell membranes, nerve cells that wrap selulubung nerve cells and bile. In addition to fat, there are also other lipid classes that are not related to fatty acids but are still classed as fat because it has properties similar to the actual fat. The same substance is known as lipomimetic compoud, ie components that resemble fat. For example, cholesterol. Cholesterol is a natural substance with physical properties such as fat but have a formula like steroida (Tjay, 2002). Cholesterol is present in tissues and plasma lipoproteins, which can be in the form of free cholesterol or combined with long-chain fatty acids as an ester kolesteril. This element is synthesized in many tissues from acetyl-CoA and eventually expelled from the body in the bile as cholesterol or bile salts. Cholesterol is the precursor of all other steroid compounds within the body, eg, corticosteroids, sex hormones, bile acids and vitamin D (Murray, 2003).

Cholesterol biosynthesis can be divided into five stages as follows:
1. Mevalonic, which is a six-carbon compound, synthesized dariasetil- CoA.
2. Isoprenoid units formed from mevalonic to remove CO2.
3. Six units held isoprenoid condensation to form skualen.
4. Skualen undergo cyclization to produce the parent steroid compound, namely lanosterol.
5. Cholesterol is formed from lanosterol after going through a few more stages Furthermore, including removing three methyl groups (Murray, 2003).

Nicotine

NICOTINE

The molecular formula C10H14N2 Nicotine, an active component of the primary pharmacological tobacco, Nikotiana tabacum. It was also found in large quantities in other species in the family solanaceae such as tomatoes, potatoes, and green pepper aubergin (Sarker, 2007). Based on the true alkaloids including N atoms. Physical Chemistry The hygroscopic oily liquid, mixed with water in the form of free base or in the form of salts. Having two nitrogen ring systems: one is pyridine and the other is pyrrolidine, so it can be grouped in pyridine and pyrrolidine alkaloids. (Sarker, 2007)
Biosynthesis

Dangers of nicotine in cigarettes, here I will explain what it is and what impact nicotine nicotine use.

- Addicted to nicotine in cigarettes equal addiction to heroin or cocaine.

- More younger you start smoking cigarettes, the more robust flavor your craving to smoke.

- Most of the drug users and alcohol stems from smokers.

Nicotine is a poison that acts directly to the brain, damaging thoughts and body. If you smoke, you will be dependent on nicotine. Without cigarettes, you experience symptoms that are less palatable for example, you might:

Feeling irritable, hollow or furious.

Anxious or agitated.

Stress at work.

The relief that you enjoy from each cigarette is only temporary and the symptoms will return the original. You will then be lit another cigarette again, and not long after, you become addicted to nicotine.

Nicotine slowly will result in changes in the brain cells of smokers who cause you feel the need to smoke more to cope with withdrawal symptoms.

Nicotine is a powerful addictive! Nicotine cigarettes contain more addictive substances (substances that cause addiction) than heroin or cocaine. The tobacco companies often manipulate nicotine levels in cigarettes they produce in order to give a sense of the same. They also can not ensure the same level of nicotine in each cigarette you suck.

Nicotine cigarettes, just seconds after the first puff, begin to affect the central nervous system and the rest of your body. In certain parts of the brain, after being exposed to nicotine stimulation, you will be able to think more lightly. Another part of the brain, which is the center of "pleasure", when stimulated nicotine can make you feel more relaxed and comfortable, free from tension.

Cigarette Nicotine also affects the hormones produced by the body. This is done by hormones to make the chemical balance of the nicotine addiction and the accompanying. Heavy smokers will become dependent on the hormone levels are very high, caused by nicotine, which can be a very powerful addictive substance. They need to smoke a cigarette with a certain time interval. After the stimulation of hormones decreases, they will need another cigarette to smoke in order to feel good / better.

Nicotine cigarettes would create biochemical reactions in your body, which quickly gives effect to the 'mood', your body's metabolism and ability to act. The more smoke you breathe, the more your body's chemical dependency. Smokers can also become addicted to cigarettes are always dependent on the psychological effects caused by induced nicotine. If this happens, smoking will be able to influence the attitudes and feelings in certain situations.

Nicotine cigarettes can respond to brain to the body makes substances more endorphins. Endorphins are protein compounds or rather the body's natural pain killer. Endorphins chemical structure similar to morphine which is a painkiller upscale. Endorphins can make a person feel relaxed and euphoric.

Nicotine cigarettes in the long run may increase cholesterol levels in the blood that cause the smoker (quit smoking even after a long time) are very susceptible to strokes and heart attacks. This is due to damage of the arteries in the blood, which is one of its functions to circulate oxygen throughout the body.

Effect of Nicotine Cigarette in humans

And if they can not get to smoked another cigarette, then the addiction begins ... let's quit smoking.

Journey nicotine,

Why is nicotine harmful? Nicotine is the substance in the release when a person smokes. So if we buy a pack of cigarettes, there would be no explanation of nicotine and tar. Nicotine is the most addictive than drugs - other medicines. One of the most widely abused drug use is nicotine, which can come from smoking or chewing tobacco. Journey nicotine from the lungs - lungs to the brain fairly quickly at only 7 seconds. After reaching the brain nicotine stimulates the release of dopamine, an important neurotransmitter involved in mood (mood), appetite and other brain functions. When a person smokes, the nicotine will enter and begin to accumulate in the body. Eventually someone is going to get used to the nicotine and if he does not get the same amount, the body will ask for more. And usually the amount of nicotine that goes will be greater or increased.

Users can quickly become nicotine dependent, because it only takes a few cigarettes to be able to make a person has an addiction. If someone arrives - arrives to stop smoking, then it will have the effect of reversal (withdrawal effect) such as anxiety and mood swings.

One of the things that can not be denied is nicotine addiction usually begins in one try - try or experiment with cigarettes. In many cases this condition sometimes been started since someone still in school or aged 13-14 years. As a pure drug, nicotine has few adverse effects to one's physical health. But the substance - other chemicals contained in cigarettes and join the nicotine is what can cause a lot of damage to the body.

Because when a cigarette burned and smoked, then there are hundreds of chemical compounds produced and a greater risk to health. Nicotine initially discovered by besarPrancis ambassador, Jean Nicot in mid XIV century. At that time people believed nicotine as a drug. Half a century later it was discovered the dangers of nicotine to the body, but only a few people are able to say no to nicotine.

MID TEST NATURAL PRODUCT OF CHEMISTRY

NAME : ELSA YANTI MALA
NIM    : RSA1C110010
MID TEST : NATURAL PRODUCT OF CHEMISTRY

1. kemukakan gagasan ANDA bagaimana Cara mengubah suatu senyawa BAHAN alam Yang tidak Punya Potensi (tidak Aktif) dapat dibuat menjadi senyawa Unggul Yang memiliki Potensi aktifitas biologis Tinggi. Berikan Contoh

2. jelaskan bagaimana idenya suatu senyawa BAHAN alam Yang memiliki Potensi biologis Tinggi, Dan Prospektif untuk kemaslahatan makhluk Hidup dapat disintesis di labortorium!

3.  Jelaskan kaidah-kaidah pokok dalam memilih pelarut  untuk isolasi dan purifikasi suatu senyawa bahan alam. Berikan dengan contoh untuk 4 golongan senyawa bahan alam : terpenoid, alkaloid, flavonoid dan steroid !

4.  jelaskan dasar titik tolak penentuan struktur suatu senyawa organic. Bila senyawa bahan alam tersebut adalah kafein misalnya. Kemukakan gagasan anda tentang hal-hal pokok apa saja yang diperlukan untuk menentukan struktur secara keseluruhan !

1.     Bioaktifvity by testing it and by doing some research to synthesize these compounds. Reacting with other compounds that can produce useful products. Isolation of Active Compounds example Efficacious Cytotoxic Flavonoids from Leaves Kemuning (Murraya Panicullata L. Jack) 1 gram fraction of methanol extract yellow leaves, flavonoids derived class of flavones (apigenin) as light yellow crystals of yellow leaves with a melting point (195-196o C). From the test results Brine Shrimp Lethality Test against these compounds are not toxic effect on larvae of Artemia salina Leach with LC50 194.786 ug / ml.

2.     the idea of a compound of natural ingredients that have a high biological potency and prospective for the benefit of sentient beings can be synthesized in the lab, in my opinion is a way to extract in vivo, such as tea leaf extract as a cancer drug that can be useful to society. It can also be synthesized in the laboratory to produce useful products.

For example, quercetin found in parasites that developed as an anticancer agent:

Parasite plants that had only known as weeds or parasitic on other plants as anticancer compounds known abortion will then need to inform the general public of these properties. Penginformasian in the community also needs to be accompanied by information on how to utilize the parasite simply as a traditional or herbal medicine, both its manufacture and its use.

With the data that the parasite tea (Scurrula oortiana) has entered the list of candidates the opportunity fitofarmaka other parasites are still one family with tea parasite to develop a greater fitofarmaka such parasites mango (Dendrophthoe pentandra). It is supported in terms of toxicity, where both parasites are relatively non-toxic. In mango parasites obtained by false LD50 16, 0962 g / kg for mice (Khakim, 2000), LD50 of parasite tea> 5 g / kg bw (Winarno, 2000). When viewed from kuersetinnya levels, the parasite is more promising as mango tea parasite because fitofarmaka than quercetin levels of parasite mango of 39.8 mg / g higher than the tea parasite levels reached only 9.6 mg / g (Rosidah, et al. , 1999). With the content of quercetin are much larger than the parasite mango tea parasite has its own economic value to be used as fitofarmaka.

Several studies have been conducted on the parasite mango as a first step towards fitofarmaka include phytochemical studies to identify the active compound content. From experiments it is known that the parasite mango contains flavonoids quercetin, meso-inositol, rutin, and tannins (Lestyorini, 2007). Test selectivity sitotoksitas mango parasites showed that the concentration of 100 ppm both ethanolic extracts and water extracts showed no cytotoxic to normal cells (cell viability B16 <0%) (Artanti, et al., 2003). Acute toxicity test was not obtained dose mango parasite that causes the death of test animals, so it can only be found false LD50 for mice of 16.0962 g / kg (Khakim, 2000). Pharmacological test showed that the parasite isolates mango flavonoids have inhibitory activity of cancer growth in mice at a dose of 12.2 mg / ml (Sukardiman, 1999). Pharmacological trials on potential, efficacy, as well as the activity of the parasite mango quercetin has also been carried out in combination with chemotherapeutic agents such as mentioned above.

Having conducted a series of studies, the direction of parasite mango fitofarmaka clearer. However, to realize the parasite mango as fitofarmaka still needed a long stride. Apart from having to determine the formula, and the formula confirmation of identity, must be carried out clinical trials on humans. As a traditional medicine that will move towards phytopharmaca course required no small cost. The solution offered is made ​​mango parasite Standardized Herbal Medicines (OHT) first. If this is done, then it will obviously give a positive value for the development of fitofarmaka. Costs can be reduced in such a way as some steps tests have been done, such as the standardization of the content and clinical trials. In addition to the parasite as OHT maketh the publication of the public about the benefits of the parasite can also be achieved.

3. Examples of the four classes of compounds of natural ingredients:

a. flavonoids

For Flavonoids solvent used is usually n-hexane, methanol. for non-polar flavonoids (eg, isoflavones, flavanones, flavones and flavonols alcohol) was extracted using non-polar solvents as well as chloroform, dichloromethane, diethyl ether, or ethyl acetate. For example Isolation Efficacious Compounds Active Cytotoxic Flavonoids from Leaves Kemuning (Murraya Panicullata Jack L.) using solvent n-hexana

b. terpenoids

usually with the solvent methanol. Election methanol solvent in this process because it has the properties of materials that will easily dissolve in the solvent extract Elections and methods appropriate for the purposes of isolation is absolutely necessary, therefore the choice of solvent is used to determine the success in isolation. Phenolic compounds are compounds that are polar and soluble in polar and semipolar solvents, the research will be conducted using the solvent ethyl acetate is polar. For example extracts ISOLATION OF COMPOUNDS terpenes Aglaia odorata Lour SKIN STEM (Meliaceae) using the solvent ethyl acetate

c. alkaloids

usually use organic solvents such as chloroform, ether, etc., eg flavonoids isolated with petroleum ether solvent

d. steroids

commonly used solvents are polar and semi-polar, it can be used solvent ether or chloroform. Examples of steroid compounds isolated from the bark of plants maja using the solvent n-hexana.

4. Before the beginning of the structure determination of spectroscopic techniques are introduced, namely the first half of the 20th century, the structure determination of organic compounds based on a comparison with compounds whose structures are known. When all the physical and chemical properties of compounds identical to compounds that have been described in the literature, it can be concluded that the compound under study is identical to the structure snyawa known. This criterion was adopted until now although the comparison is done may be different. When the physical and chemical properties of the investigated compounds are not appropriate with any compound that are well known in the literature, the possibility of this compound is a new compound, has never been synthesized or has not been reported. In such cases, new problems may arise. How can one determine the structure of an entirely new compound? The method for determining the structure changed dramatically in the mid-20th century. Traditional method, although simple, is very time consuming and difficult in practice: thus, the first structure of a newly synthesized compound is assumed, and then a particular route is designed to convert these compounds into compounds known. Changing it may require several steps. Throughout the structural changes caused by each identified stage, the successful conversion to a known compound is a testament to the assumed structure. It should be added that the reaction to the change of the selected reaction involves only the functional groups and not the framework of the molecule.

Spectroscopic methods is a key tool in modern chemistry for the identification of the molecular structure. In organic chemistry, spectroscopic methods used to determine and confirm the molecular structure, to monitor the reaction and to determine the purity of a compound. The most important method for organic chemistry is a core magetik resonance spectroscopy: 1H and 13C NMR spectroscopy, mass spectrometry, infrared spectroscopy and UV / Vis.

example:

  IDENTIFICATION OF COMPOUNDS terpenes extract Aglaia odorata Lour SKIN STEM (Meliaceae)

Phase identification of the isolated compounds

Determination of molecular structure by sticher in [17] the determination of molecular structures obtained through spectroscopic measurement steps to obtain spectral data. After obtaining the spectral data of new molecular structures determined. The steps were as follows:

1. To measure the UV-Vis spectra to determine the chromophore groups

2. To measure the IR spectrum for the presence of functional groups

3. To measure the mass spectra (MS) to determine the fragmentation pattern of the compound.

Phase identification of compounds

identification isolat_I

Then on Isolat_I performed include identification of chemical test, test and test physics spectroscopy. Chemically test is performed using FeCl3 and Shinoda test. From the test results it is known that chemical compounds are included into the Isolat_I Phenolics. That is indicated by the color change to yellow.

While the identification through a physical test conducted by examining the melting point Isolat_I. From the test results using Electrothermal Melting Point Apparatus with repetition three times, known melting point of isolates I, the 120-121oC, 120-121oC, 120-122oC. From these measurements it can be seen that the measurement of the melting point at the beginning and end of the show the differences that do not exceed 1.

In the UV-Vis spectroscopy test the samples were dissolved in methanol obtained maximum absorption at = 278 and 338 nm

Test results on UV-Vis Isolat_I known that maximum absorption at α = 278 and 338. Predictably a saturated ketones and aldehydes. Saturated ketones and aldehydes showed a weak symmetry forbidden bands at 275-295 nm, ε ~ 20, is the result of the excitation of electrons to oxygen silent anti-bonding orbital of the carbonyl group. Ketones and aldehydes substituted more strongly absorbed in the upper area. The existence of weak bands in the 275-295 nm region is indicative of the carbonyl group of ketones or aldehydes [12]. Ketone α, β-unsaturated show ribbons n   π * little stronger or a series of bands with ε ~ 100 at 300-500 nm. Transition n   π * α-diketon diketon form shows two bands, one in the region near 290 nm, ε ~ 30 and ε 10-30 second tape appeared on the visible region at 340-400 nm.

In IR spectroscopy tests, measurements Infrared spectra (IR) were prepared by KBr pellet technique has been shown in Figure 2. IR spectrum of the isolated compounds showed uptake in the area of ​​772, 1219, 1650, 2854, 2922, 3435 cm-1. The tops of the show include: aromatic CC absorption of 860-680 cm-1 for the peak 772, uptake of CO 1260-1000 cm-1 for the top of 1219, then C = C aromatic absorption at 1650 cm-1 peak, at the peak of the aliphatic CH 2854, and at the height of 2922 showed strong CH absorption from 2850 to 2970, and the last in 3435 showed peak OH absorption at 3200-3600.

From the results of GC-MS spectroscopy testing Isolat_I consists of 17 dominant peaks (Fig. 3), the dominant peak of 17 was then carried out the mass spectrometry data retrieval as much as 3% of the area that has a peak above 4.00% is the peak number 2, 3, and 6 ..

From the top 2, unknown compounds can be demonstrated in isolates I-stem molecular ion peak at m / z, namely: 147, 138, 123, 109, 96, 81, 67, 43, 41, 38 with the base peak at m / z 43. From the results of the study of literature and to help chemoffice compounds with peaks as mentioned meurpakan characteristic peaks at sesquiterpene compound [13] that this compound is a compound suspected sesquiterpene epoxy type II humulen molecular weight 220, can be seen in Figure 4. This compound underwent termination of m / z 220 produced m / z 149 by releasing C5H11 `. Then proceed with the loss of C2H2 and CH2 resulting fragment m / z 123 and 109. Further loss of CO fragments m / z 81 (C6H9 +), the next result in fragment m / z 67 (C5H7 +) with CH2 and final disappearance of fragments m / z 41 (C3H5 +). While at the height of 3, were found to have molecular ion peaks at m / z 205, 187, 177, 162, 147, 121, 107, 93, 79, 67, and a base peak at m / z 43. The compound has a bicyclic sesquiterpenes fragmentation peaks at m / z 43, 55, 69, 81, 121, 133, 149, 191, 205 and 234 [M +] with a base peak at m / z 43 [14]. Several studies cite leteratur isoprenoid compounds give m / z at 69 for isoprene, m / z 137 for monoterpenes, and m / z 205 for sesquiterpene [15]. This compound has a molecular weight of 205. From the literature study, this compound was found in plants Ophiopogon snack Lodd At the top 6, it is known that compounds having an breakdown fragment at m / z 279, 168, 167, 149, 132, 113, 104, 84, 71, 57, 41 and 39 , with a base peak at m / z 149. From the results of IR spectroscopy, UV-Vis and GC-MS. Compounds Isolat_I with Mr = 279 is thought to be the compound α-santalan-type sesquiterpene. It is based on the results of IR spectroscopy Isolat_I alleged resemblance to the results of IR-santalan compound α-sesquiterpene [16], can be seen in table 1. In the MS spectrum of the peak Isolat_I no 6, shows that the m / z of 279 or Mr. Then from that spectrum MS-sesquiterpene α-santalan also showed m / z or Mr at (279 [M +-CH3], 164, 121, 59). These compounds undergo chain termination epoxy and ether on one side so as to produce m / z 167 (M +1- C4H7O + - C3H7 +, C11H19O +). Then followed by the disappearance of the H2O fragment m / z 167 fragments stable at m / z 149 (C11H17 +). Fragments generated when removing the epoxide and propyl chain fragments m / z 71 (C4H7O +) and m / z 43 (C3H7 +). In the next fragment solution if m / z 149 loses CH2 +2 H + will appear fragment m / z 132. This compound has a molecular weight of 279.

terpenoids

I. Terpenoids

In plants there are usually hydrocarbons and oxygenated hydrocarbons which are terpenoid compounds. Words terpenoid compounds include a large number of plants, and the term is used to indicate that the biosynthesis of all plant compounds that come from the same compound. So, all terpenoids derived from isoprene molecules CH2 == C (CH3) == CH2 and CH ─ carbon frame built by connecting 2 or more units of this C5. Then the compounds are broken into several categories based on the number of units contained in the compound, 2 (C10), 3 (C15), 4 (C20), 6 (C30) or 8 (C40).
Terpenoids composed of several kinds of compounds, ranging from volatile oil components, namely monoterpena and sesquiterepena volatile (C10 and C15), diterpena evaporates, the triterpenoids and sterols (C30), and carotenoid pigments (C40). Each class of terpenoids are important, both in growth and metabolism as well as the ecological tumbuha. Terpenoids are isoprene units (C5H8). Terpenoids is a compound derived carbon skeleton of the six units of isoprene biosynthesis and cyclic C30 hydrocarbons derived from the skualena. This compound is a relative cyclic complex structure, mostly in the form of alcohol, aldehyde or carboxylic atom. They form colored compounds, crystalline, high melting point and is often active optic characterized generally difficult because there is no chemical reactivity.

A.  Synthesis of terpenoid

  In general, the biosynthesis of terpenoids three basic reactions, namely:

1. Formation of active isoprene derived from acetic acid via mevalonic acid.
2. Merging head and tail isoprene units to form mono-, seskui-, di-, Sester-, and poly-terpenoids.
3. The incorporation of the tail and the tail unit C-15 or C-20 produces triterpenoids and steroids.

acetic acid after being activated by coenzyme A did produce acid Claisen type condensation asetoasetat. Compounds produced by the condensation of acetyl coenzyme A did produce aldol type branched carbon chains as found in mevanolat acid. Subsequent reactions is phosphorylation, elimination of phosphoric acid and subsequent decarboxylation produces IPP to DMAPP by the enzyme berisomerisasi isomerase. IPP as active isoprene units joined to the tail with DMAPP and this merger is the first step of the polymerization of isoprene to produce terpenoids. This merger occurs because electrons attack the double bond carbon atoms of IPP to DMAPP electron deficient ison followed by removal of pyrophosphate. These attacks result in geranil pyrophosphate (GPP), which is an intermediate for all compounds monoterpenes.
Subsequent incorporation between the IPP and GPP unit, with the same mechanism as the IPP and DMAPP, produce farnesil pyrophosphate (FPP), which is an intermediate compound for all sesquiterpene compound. Compounds derived diterpene geranil geranil-pyrophosphate (GGPP) derived from the condensation between the units or IPP and GPP by the same mechanism as well.
 

When organic reactions are listed in Figure 2 explored more deeply, it turns out that the synthesis of terpenoids by a simpler organism is very nature. In terms of the theory of organic synthesis reaction is only using a few basic types of reactions. Subsequent reactions of the compounds between GPP, FPP and GGPP to produce terpenoid compounds one by one just involves some kind of secondary reactions as well. These secondary reactions are typically hydrolysis, cyclization, oxidation, reduction and spontaneous reactions that can take place easily in a neutral atmosphere and at room temperature, such as isomerization, dehydration, decarboxylation, and so on.

 

 

. From the equation above shows that the formation of monoterpenes compounds and compounds derived from the incorporation of 3.3 terpenoida allil dimethyl pyrophosphate with isopentenyl pyrophosphate.
In general, terpenoids composed of the elements C and H with the general molecular formula (C5H8) n.
Classification is usually dependent on the value of n. 

Nama	Rumus	Sumber
Monoterpen	C10H16	Minyak Atsiri
Seskuiterpen	C15H24	Minyak Atsiri
Diterpen	C20H32	Resin Pinus
Triterpen	C30H48	Saponin, Damar
Tetraterpen	C40H64	Pigmen, Karoten
Politerpen	(C5H8)n  n  8	Karet Alam

From the formula above most terpenoids containing carbon atoms whose numbers are multiples of five. Subsequent investigation showed also that most of the carbon skeleton terpenoids have built by two or more units called C5 isoprene unit. Unit C5 is so named because its carbon skeleton as compound isoprene. Wallach (1887) says that the skeletal structure of terpenoids constructed by two or more molecules of isoprene. This argument is known as the "law of isoprene".

B. Uses terpenoids
Uses of plant terpenoids, among others:
a. Fitoaleksin
    Fitoaleksin is an anti-microbial compound that dibiosintesis (created) and accumulated by plants after   infection of pathogenic microorganisms or exposure to certain chemicals and radiation with UV light.
b. Insect antifectan, repellant
c. Immune from herbifora
d. Pheromones plant hormones.
Pheromones are a type of chemical that serves to stimulate and have sex attractiveness in males and females].
Bioactivity terpenoids in roots and leaves of Jatropha gaumeri (distance). Because this plant terpenoids contained the compound and also in the leaf extracts have antibacterial and antioxidant activity. Activity is produced by the isolation and identification of the root that produces 2-epi-jatrogossidin (1). One was a rhamnofolane diterpene with antimicrobial activity, and both 15-epi-4E jatrogrossidentadione (2), a diterpene lathyrane without biological activity. In the same way, the purification of the studies that have been tested from the leaf extract may identified sitosterol and triterpene amaryn, traraxasterol. These metabolites it can be used as antioxidant activity.