Identification of Chemical Compound of Dammar Resin using Various Solvents with Gas Chromatographic Mass Spectrometric Method Jamal I.N.G. Wardana Nurkholis Hamidi Denny Widyanuriawan September 22-26, 2014 WVCARMEA 2014 UTM, Johor, Malaysia
Introduction Dammar resin trees mostly grow and deploy in tropical countries. Dammar resins that are yielded from tapping are classified as non-wood forest prominent products that are found a lot in Krui (Indonesia). Applications of dammar resin has been implemented and its application can be optimally used including as a source of alternative renewable fuel energy. To optimize the application, it is necessary to identify the chemical compound that may be contained in dammar resin.
Introduction Gas Chromatographic-Mass Spectrometric (GC-MC) method was carried out to validate the chemical compound of dammar resin where from the experiment Identification of dammar resin potency for alternative renewable fuel energy can be known.
Materials Dammar resin (Shorea Javanica k. et v.) is obtained from tapping of the dammar tree. The yellowish brass color was selected from the tree with dimension that larger than 3 cm 3. There are four solvents used; chloroform (CHCl 3 ), hexane (C 6 H 14 ), ethyl acetate (CH 3 COOH) and methanol (CH 3 OH).
Materials
Methods The dammar resin chemical compound is determined from analysis of GC-MS method using Agilent 7890A Gas Chromatograph. There is a library for automatic sample on Agilent 7890A for sample introduction. The sample of dammar resin is dissolved in solvent material that was injected by about 0,5 ml. The carrier gas is Helium. Injector temperature of Gas Chromatograph is 280 C. The oven temperature is kept on 70 C for 5 minutes. After that, oven is heated with heat ratio of 10,0 C/minute until 300 C. The last oven temperature is kept constant on 300 C for 5 minutes.
Methods The yielded mass spectrogram is matched by instrument and automatically converted into certain compound based on similarity pattern of its m/z with mass spectrograms that are already installed in instrument s database. The installed mass spectrograms are NIST (National Institute of Standards and Technology) and W8N05ST (database Agilent 7890A). The component percentage of dammar is calculated based on ratio of peak area of each component into all peak areas of all components in the chromatogram.
Results
Results From Figure, it can be seen that GC-MS reading result shows that dammar resin with CHCl 3 giving graph results similar with reading results of C 6 H 14, however, reading results of GC-MS giving very different result when dammar resin applied with CH 3 COOH and CH 3 OH. C 6 H 14 also gives different result with the previous solvents. The reading results show similarity only for CH 3 COOH and CH 3 OH.
Discussion From table 1, there are 32 chemical compound are detected from dammar resin that is dissolved in CHCl 3 using GC-MS experiment method. Table 1. Chemical compound of dammar resin from GC-MS result with CHCl 3 Chemical compound Formula % 1R-α-Pinene C 10 H 16 1.12 3-Carene C 10 H 16 0.82 β Fenchyl alcohol C 10 H 18 O 0.83 Caryophyllene C 15 H 24 0.43 Trans-γ-bibabolene C 15 H 24 0.80 Cholesterol C 27 H 46 O 17.93 2,6-Di (t-butyl)-4-hydroxybenzaldehyde C 15 H 22 O 2 0.40 7,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione C 17 H 24 O 3 0.83
Discussion Chemical compound Formula % cis-3a,4,5,6,7,7a-hexahydro-5-(3-hydroxypropyl)-5-methyl-1hinden-1-one C 13 H 20 O 2 0.82 2-(4'-Methoxyphenyl)-2-(2'-methoxyphenyl)propane C 17 H 20 O 2 0.80 Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a-dodeca- C 19 H 28 0.66 hydro-4a,7-dimethyl-1-methylene-,[4as-(4aα,4aβ,7β,10aβ)]- Epicodisterol C 28 H 46 O 6.68 2,3,4-Trimethoxyphenylacetonitrile C 11 H 13 NO 3 1.86 2,5-di-tert-Butyl-1,4-benzoquinone C 14 H 20 O 2 1.39 Androst-16-en-3-one, (5α)- C 19 H 28 O 1.11 2-acetyl-4-(2,5-dichlorophenyl)furan C 12 H 8 Cl 2 O 2 0.59 Lumiflavine C 13 H 12 N 4 O 2 0.79 Dehydrocacalohastin-14-ol C 16 H 16 O 3 0.82 10,11-Dihydrobenzo[k]fluoranthene C 20 H 14 3.41
Discussion Chemical compound Formula % Benzo[h]quinoline, 2,4-dimethyl- C 15 H 13 N 0.37 1,2-Bis(trimethylsilyl)benzene C 12 H 22 Si 2 0.93 methyl 1-methyl-3-propyl-9H-carbazole-2-carboxylate C 18 H 19 NO 2 0.60 1-Methyl-oestra-1,3,5(10)-trien-18-nor-17-ketone C 18 H 22 O 2.00 [1,1'-Biphenyl]-4-amine, 4'-fluoro- C 12 H 10 FN 18.27 6 methyl-2 phenylindole C 15 H 13 N 0.55 Silane, 1,4-phenylenebis[trimethyl- C 12 H 22 Si 2 1.10 Tetrasiloxane, decamethyl- C 10 H 30 O 3 Si 4 1.85 1,1,1,3,5,5,5-Heptamethyltrisiloxane C 7 H 22 O 2 Si 3 6.08 Silane, trimethyl[5-methyl-2-(1-methylethyl)phenoxy]- C 13 H 22 OSi 1.38 Trimethyl(4-tert.-butylphenoxy)silane C 13 H 22 OSi 1.93 Trimethyl[4-(2-methyl-4-oxo-2-pentyl)phenoxy]silane C 12 H 18 O 2 Si 0.63 γ-sitosterol C 29 H 50 O 22.22
Discussion Dissolved in C 6 H 14 (table 2), there are 25 chemical compound are detected. Table 2. Chemical compound of dammar resin from GC-MS result with C 6 H 14 Chemical compound Formula % 1R-α-Pinene C 10 H 16 3.70 3-Carene C 10 H 16 2.40 3-Cyclohexene-1-methanol, α,α4-trimethyl- C 10 H 18 O 2.64 Caryophyllene C 15 H 24 1.75 1H-Benzocycloheptene, 2,4a,5,6,7,8-hexahydro-3,5,5,9- C 15 H 24 3.02 tetramethyl-, (R)- 7,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione C 17 H 24 O 3 2.29 Methyl 2-[1-(4-methylphenyl)hydrazine]-2-one C 13 H 21 NO 1.96
Discussion Chemical compound Formula % 2,5-di-tert-Butyl-1,4-benzoquinone C 14 H 20 O 2 3.54 Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a- C 20 H 32 2.51 dodecahydro-1,1,4a,7-tetramethyl-, [4aS-(4aα,4bβ,7β,10aβ)]- Silane, 1,4-phenylenebis[trimethyl- C 12 H 22 Si 2 2.80 12-methoxy-19-norpodocarpa-3,5,8,11,13-pentaen-7-one C 17 H 18 O 2 4.22 10,11-Dihydrobenzo[k]fluoranthene C 20 H 14 4.70 N-Methyl-1-adamantaneacetamide C 13 H 21 NO 7.15 Cyclotrisiloxane, hexamethyl- C 6 H 18 O 3 Si 3 3.66 1-Methylethyl-oestra-1,3,5(10)-trien-18-nor-17-ketone C 18 H 22 O 4.42 3,4-Dimethyl-5-(3-methylphenyl)isoxazole C 12 H 13 NO 15.40 2,4,6-Cycloheptatrien-1-one, 3,5-bis-trimethylsilyl- C 13 H 22 OSi 2 1.08
Discussion Chemical compound Formula % Benzene, 1,4-bis(trimethylsilyl)-cyclotrisiloxane, hexamethyl- C 12 H 22 Si 2 2.13 Acetic acid, [4-(1,1-dimethylethyl)phenoxy]-, methyl ester C 13 H 18 O 3 13.08 6 Methyl-2 phenylindole C 15 H 13 N 1.66 Silane, trimethyl[5-methyl-2-(1-methylethyl)phenoxy]- C 13 H 22 OSi 2.10 Trymethyl[4-(2-methyl-4-oxo-2-penthyl)phenoxy]silane C 15 H 24 O 2 Si 9.41 Trimethyl[4-(1,1,3,3,-tetramethylbutyl)phenoxy]silane C 17 H 30 OSi 1.38 1,2-Bis(trimethylsilyl)benzene C 12 H 22 Si 2 1.42 5-Methyl-2-trimethylsilyloxy-acetophenone C 12 H 18 O 2 Si 1.59
Discussion GC-MS could detect about 17 chemical compound of dammar resin when dissolved in CH 3 COOH (table 3). Table 3. Chemical compound of dammar resin from GC-MS result with CH 3 COOH Chemical compound Formula % α-pinene C 10 H 16 10.80 3-Carene C 10 H 16 8.62 Limonene C 10 H 16 2.21 Cyclohexene, 1-methyl-4-(1-methylethylidene)- C 10 H 16 3.67 3-Cyclohexen-1-ol, 4-methyl-1-(1-methylethyl)- C 10 H 18 O 1.40 3-Cyclohexene-1-methanol, α,α4-trimethyl- C 10 H 18 O 3.51 Caryophyllene C 15 H 24 4.20
Discussion Chemical compound Formula % 1H-Benzocycloheptene, 2,4a,5,6,7,8-hexahydro-3,5,5,9- C 15 H 24 5.92 tetramethyl-, (R)- Tetrasiloxane, decamethyl- C 10 H 30 O 3 Si 4 2.00 3-Methyl-5-diphenyldihydrafuran C 17 H 16 O 1.78 2-Hydroxy-12-methosy-19-norpodokarpa-1,8,11,13-tetraen-3-one C 17 H 20 O 3 3.46 12-methoxy-19-norpodocarpa-3,5,8,11,13-pentaen-7-one C 17 H 18 O 2 2.28 2,2-Dimethyl-6-acethyl-3,4-dihydronaphtho[1,2-b]pyrane C 17 H 18 O 2 2.60 1H-Indole, 1-methyl-2-phenyl- C 15 H 13 N 3.98 Retinol C 20 H 30 O 23.22 1,3-Dimethyl-4-azaphenanthrene C 15 H 13 N 13.87 Acetamide, N-[4-(trimethylsilyl)phenyl]- C 11 H 17 NOSi 6.50
Discussion From table 4, there are 15 chemical compound are identified from dammar resin when dissolved in CH 3 OH. Table 4. Chemical compound of dammar resin from GC-MS result with CH 3 OH Chemical compound Formula % α-pinene C 10 H 16 7.15 3-Carene C 10 H 16 5.63 Cyclohexene, 1-methyl-4-(1-methylethylidene)- C 10 H 16 2.15 3-Cyclohexene-1-methanol, α,α4-trimethyl- C 10 H 18 O 3.12 Caryophyllene C 15 H 24 4.14 Trans-γ-bisabolene C 15 H 24 5.43 ent-pimara-8(14),15-diene C 20 H 32 2.49
Discussion Chemical compound Formula % Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a- C 20 H 32 4.95 dodecahydro-1,1,4a,7-tetramethyl-, [4aS-(4aα,4bβ,7β,10aβ)]- Isomaturnin C 16 H 14 O 3 3.12 10,11-Dihydrobenzo[k]fluoranthene C 20 H 14 3.08 Acetamide, N-[4-(trimethylsilyl)phenyl]- C 11 H 17 NOSi 8.35 Retinol C 20 H 30 O 25.32 Methyl 3-bromo-1-adamantaneacetate C 13 H 19 BrO 2 18.18 p-trimethylsiloxybenzaldehyde oxime, trimethylsilyl- C 13 H 23 NO 2 Si 2 4.59 Propiophenone, 2'-(trimethylsiloxy)- C 12 H 18 O 2 Si 2.29
Discussion Chemical compounds yielded from dammar resin are different with four various solvents, however, there is no one of those four solvents could detect all contained chemical compounds from other solvent. Therefore, all these four solvents must be applied to detect all the contained chemical compounds of dammar resin. Based on the reading results of GC-MS, we obtained that hydrocarbon chains contained in dammar resin are potential to be used as fuel, and various bond carbon in dammar resin increasing the promising potential of dammar resin as a good source of fuel energy.
Conclusions Using GC-MS method, CHCl 3 and C 6 H 14 solvents giving similar graph and the detected chemical compound are relatively similar. Using CH 3 COOH and CH 3 OH also giving the similar results. The significant different results are given by other solvents besides those two previous couple solvents mentioned above. Using GC-MS method, it was detected about 32 and 25 chemical compounds when using CHCl 3 and C 6 H 14 respectively. Meanwhile, there were 17 and 15 chemical compounds detected when using CH 3 COOH and CH 3 OH respectively.
Conclusions All these solvents giving different results, however, the results are complementing each other because there is a solvent that could detect a chemical compound where other solvents could not detect that chemical compound. Based on chemical compounds contained in dammar resin, it can be concluded that dammar resin has a promising potency to be used as alternative renewable fuel energy.
Jamal Mechanical Engineering Department