Identification of Chemical Compound ofDammar Resin using Various Solvents withGas Chromatographic–Mass Spectrometric

Method

JamalI.N.G. WardanaNurkholis HamidiDenny Widyanuriawan

September 22-26, 2014WVCARMEA 2014

UTM, Johor, Malaysia

Introduction

• Dammar resin trees mostly grow and deploy in tropicalcountries.

• Dammar resins that are yielded from tapping areclassified as non-wood forest prominent products thatare found a lot in Krui (Indonesia).

• Applications of dammar resin has been implementedand its application can be optimally used including as asource of alternative renewable fuel energy.

• To optimize the application, it is necessary to identifythe chemical compound that may be contained indammar resin.

• Dammar resin trees mostly grow and deploy in tropicalcountries.

• Dammar resins that are yielded from tapping areclassified as non-wood forest prominent products thatare found a lot in Krui (Indonesia).

• Applications of dammar resin has been implementedand its application can be optimally used including as asource of alternative renewable fuel energy.

• To optimize the application, it is necessary to identifythe chemical compound that may be contained indammar resin.

Introduction

• Gas Chromatographic-Mass Spectrometric (GC-MC)method was carried out to validate the chemicalcompound of dammar resin where from the experiment

• Identification of dammar resin potency for alternativerenewable fuel energy can be known.

• Gas Chromatographic-Mass Spectrometric (GC-MC)method was carried out to validate the chemicalcompound of dammar resin where from the experiment

• Identification of dammar resin potency for alternativerenewable fuel energy can be known.

Materials

• Dammar resin (Shorea Javanica k. et v.) is obtainedfrom tapping of the dammar tree. The yellowish brasscolor was selected from the tree with dimension thatlarger than 3 cm3.

• There are four solvents used; chloroform (CHCl3),hexane (C6H14), ethyl acetate (CH3COOH) andmethanol (CH3OH).

• Dammar resin (Shorea Javanica k. et v.) is obtainedfrom tapping of the dammar tree. The yellowish brasscolor was selected from the tree with dimension thatlarger than 3 cm3.

• There are four solvents used; chloroform (CHCl3),hexane (C6H14), ethyl acetate (CH3COOH) andmethanol (CH3OH).

Materials

Methods

• The dammar resin chemical compound is determinedfrom analysis of GC-MS method using Agilent 7890AGas Chromatograph. There is a library for automaticsample on Agilent 7890A for sample introduction.

• The sample of dammar resin is dissolved in solventmaterial that was injected by about 0,5 mL. The carriergas is Helium. Injector temperature of GasChromatograph is 280 °C. The oven temperature is kepton 70 °C for 5 minutes. After that, oven is heated withheat ratio of 10,0 °C/minute until 300 °C. The last oventemperature is kept constant on 300 °C for 5 minutes.

• The dammar resin chemical compound is determinedfrom analysis of GC-MS method using Agilent 7890AGas Chromatograph. There is a library for automaticsample on Agilent 7890A for sample introduction.

• The sample of dammar resin is dissolved in solventmaterial that was injected by about 0,5 mL. The carriergas is Helium. Injector temperature of GasChromatograph is 280 °C. The oven temperature is kepton 70 °C for 5 minutes. After that, oven is heated withheat ratio of 10,0 °C/minute until 300 °C. The last oventemperature is kept constant on 300 °C for 5 minutes.

Methods

• The yielded mass spectrogram is matched byinstrument and automatically converted into certaincompound based on similarity pattern of its m/z withmass spectrograms that are already installed ininstrument’s database. The installed massspectrograms are NIST (National Institute of Standardsand Technology) and W8N05ST (database Agilent7890A). The component percentage of dammar iscalculated based on ratio of peak area of eachcomponent into all peak areas of all components in thechromatogram.

• The yielded mass spectrogram is matched byinstrument and automatically converted into certaincompound based on similarity pattern of its m/z withmass spectrograms that are already installed ininstrument’s database. The installed massspectrograms are NIST (National Institute of Standardsand Technology) and W8N05ST (database Agilent7890A). The component percentage of dammar iscalculated based on ratio of peak area of eachcomponent into all peak areas of all components in thechromatogram.

Results

Results

• From Figure, it can be seen that GC-MS reading resultshows that dammar resin with CHCl3 giving graphresults similar with reading results of C6H14, however,reading results of GC-MS giving very different resultwhen dammar resin applied with CH3COOH andCH3OH. C6H14 also gives different result with theprevious solvents. The reading results show similarityonly for CH3COOH and CH3OH.

• From Figure, it can be seen that GC-MS reading resultshows that dammar resin with CHCl3 giving graphresults similar with reading results of C6H14, however,reading results of GC-MS giving very different resultwhen dammar resin applied with CH3COOH andCH3OH. C6H14 also gives different result with theprevious solvents. The reading results show similarityonly for CH3COOH and CH3OH.

Discussion

• From table 1, there are 32 chemical compound aredetected from dammar resin that is dissolved in CHCl3using GC-MS experiment method.

Table 1. Chemical compound of dammar resin from GC-MS resultwith CHCl3

• From table 1, there are 32 chemical compound aredetected from dammar resin that is dissolved in CHCl3using GC-MS experiment method.

Table 1. Chemical compound of dammar resin from GC-MS resultwith CHCl3

Chemical compound Formula %1R-α-Pinene C10H16 1.123-Carene C10H16 0.82β Fenchyl alcohol C10H18O 0.83Caryophyllene C15H24 0.43Trans-γ-bibabolene C15H24 0.80Cholesterol C27H46O 17.932,6-Di (t-butyl)-4-hydroxybenzaldehyde C15H22O2 0.407,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione C17H24O3 0.83

Discussion

Chemical compound Formula %cis-3a,4,5,6,7,7a-hexahydro-5-(3-hydroxypropyl)-5-methyl-1H-inden-1-one

C13H20O2 0.82

2-(4'-Methoxyphenyl)-2-(2'-methoxyphenyl)propane C17H20O2 0.802-(4'-Methoxyphenyl)-2-(2'-methoxyphenyl)propane C17H20O2 0.80Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a-dodeca-hydro-4a,7-dimethyl-1-methylene-,[4aS-(4aα,4aβ,7β,10aβ)]-

C19H28 0.66

Epicodisterol C28H46O 6.682,3,4-Trimethoxyphenylacetonitrile C11H13NO3 1.862,5-di-tert-Butyl-1,4-benzoquinone C14H20O2 1.39Androst-16-en-3-one, (5α)- C19H28O 1.112-acetyl-4-(2,5-dichlorophenyl)furan C12H8Cl2O2 0.59Lumiflavine C13H12N4O2 0.79Dehydrocacalohastin-14-ol C16H16O3 0.8210,11-Dihydrobenzo[k]fluoranthene C20H14 3.41

Discussion

Chemical compound Formula %Benzo[h]quinoline, 2,4-dimethyl- C15H13N 0.371,2-Bis(trimethylsilyl)benzene C12H22Si2 0.93methyl 1-methyl-3-propyl-9H-carbazole-2-carboxylate C18H19NO2 0.60methyl 1-methyl-3-propyl-9H-carbazole-2-carboxylate C18H19NO2 0.601-Methyl-oestra-1,3,5(10)-trien-18-nor-17-ketone C18H22O 2.00[1,1'-Biphenyl]-4-amine, 4'-fluoro- C12H10FN 18.276 methyl-2 phenylindole C15H13N 0.55Silane, 1,4-phenylenebis[trimethyl- C12H22Si2 1.10Tetrasiloxane, decamethyl- C10H30O3Si4 1.851,1,1,3,5,5,5-Heptamethyltrisiloxane C7H22O2Si3 6.08Silane, trimethyl[5-methyl-2-(1-methylethyl)phenoxy]- C13H22OSi 1.38Trimethyl(4-tert.-butylphenoxy)silane C13H22OSi 1.93Trimethyl[4-(2-methyl-4-oxo-2-pentyl)phenoxy]silane C12H18O2Si 0.63γ-Sitosterol C29H50O 22.22

• Dissolved in C6H14 (table 2), there are 25 chemicalcompound are detected.

Table 2. Chemical compound of dammar resin from GC-MS resultwith C6H14

Discussion

• Dissolved in C6H14 (table 2), there are 25 chemicalcompound are detected.

Table 2. Chemical compound of dammar resin from GC-MS resultwith C6H14

Chemical compound Formula %1R-α-Pinene C10H16 3.703-Carene C10H16 2.403-Cyclohexene-1-methanol, α,α4-trimethyl- C10H18O 2.64Caryophyllene C15H24 1.751H-Benzocycloheptene, 2,4a,5,6,7,8-hexahydro-3,5,5,9-tetramethyl-, (R)-

C15H24 3.02

7,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione C17H24O3 2.29Methyl 2-[1-(4-methylphenyl)hydrazine]-2-one C13H21NO 1.96

Discussion

Chemical compound Formula %2,5-di-tert-Butyl-1,4-benzoquinone C14H20O2 3.54Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydro-1,1,4a,7-tetramethyl-, [4aS-(4aα,4bβ,7β,10aβ)]-

C20H32 2.51Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydro-1,1,4a,7-tetramethyl-, [4aS-(4aα,4bβ,7β,10aβ)]-

C20H32 2.51

Silane, 1,4-phenylenebis[trimethyl- C12H22Si2 2.8012-methoxy-19-norpodocarpa-3,5,8,11,13-pentaen-7-one C17H18O2 4.2210,11-Dihydrobenzo[k]fluoranthene C20H14 4.70N-Methyl-1-adamantaneacetamide C13H21NO 7.15Cyclotrisiloxane, hexamethyl- C6H18O3Si3 3.661-Methylethyl-oestra-1,3,5(10)-trien-18-nor-17-ketone C18H22O 4.423,4-Dimethyl-5-(3-methylphenyl)isoxazole C12H13NO 15.402,4,6-Cycloheptatrien-1-one, 3,5-bis-trimethylsilyl- C13H22OSi2 1.08

Discussion

Chemical compound Formula %Benzene, 1,4-bis(trimethylsilyl)-cyclotrisiloxane, hexamethyl- C12H22Si2 2.13Acetic acid, [4-(1,1-dimethylethyl)phenoxy]-, methyl ester C13H18O3 13.086 Methyl-2 phenylindole C15H13N 1.66

13.086 Methyl-2 phenylindole C15H13N 1.66Silane, trimethyl[5-methyl-2-(1-methylethyl)phenoxy]- C13H22OSi 2.10Trymethyl[4-(2-methyl-4-oxo-2-penthyl)phenoxy]silane C15H24O2Si 9.41Trimethyl[4-(1,1,3,3,-tetramethylbutyl)phenoxy]silane C17H30OSi 1.381,2-Bis(trimethylsilyl)benzene C12H22Si2 1.425-Methyl-2-trimethylsilyloxy-acetophenone C12H18O2Si 1.59

• GC-MS could detect about 17 chemical compound ofdammar resin when dissolved in CH3COOH (table 3).

Table 3. Chemical compound of dammar resin from GC-MS resultwith CH3COOH

Discussion

• GC-MS could detect about 17 chemical compound ofdammar resin when dissolved in CH3COOH (table 3).

Table 3. Chemical compound of dammar resin from GC-MS resultwith CH3COOH

Chemical compound Formula %α-Pinene C10H16 10.803-Carene C10H16 8.62Limonene C10H16 2.21Cyclohexene, 1-methyl-4-(1-methylethylidene)- C10H16 3.673-Cyclohexen-1-ol, 4-methyl-1-(1-methylethyl)- C10H18O 1.403-Cyclohexene-1-methanol, α,α4-trimethyl- C10H18O 3.51Caryophyllene C15H24 4.20

Discussion

Chemical compound Formula %1H-Benzocycloheptene, 2,4a,5,6,7,8-hexahydro-3,5,5,9-tetramethyl-, (R)-

C15H24 5.92

Tetrasiloxane, decamethyl- C10H30O3Si4 2.00

1H-Benzocycloheptene, 2,4a,5,6,7,8-hexahydro-3,5,5,9-tetramethyl-, (R)-Tetrasiloxane, decamethyl- C10H30O3Si4 2.003-Methyl-5-diphenyldihydrafuran C17H16O 1.782-Hydroxy-12-methosy-19-norpodokarpa-1,8,11,13-tetraen-3-one C17H20O3 3.4612-methoxy-19-norpodocarpa-3,5,8,11,13-pentaen-7-one C17H18O2 2.282,2-Dimethyl-6-acethyl-3,4-dihydronaphtho[1,2-b]pyrane C17H18O2 2.601H-Indole, 1-methyl-2-phenyl- C15H13N 3.98Retinol C20H30O 23.221,3-Dimethyl-4-azaphenanthrene C15H13N 13.87Acetamide, N-[4-(trimethylsilyl)phenyl]- C11H17NOSi 6.50

• From table 4, there are 15 chemical compound areidentified from dammar resin when dissolved in CH3OH.

Table 4. Chemical compound of dammar resin from GC-MS resultwith CH3OH

Discussion

• From table 4, there are 15 chemical compound areidentified from dammar resin when dissolved in CH3OH.

Table 4. Chemical compound of dammar resin from GC-MS resultwith CH3OH

Chemical compound Formula %α-Pinene C10H16 7.153-Carene C10H16 5.63Cyclohexene, 1-methyl-4-(1-methylethylidene)- C10H16 2.153-Cyclohexene-1-methanol, α,α4-trimethyl- C10H18O 3.12Caryophyllene C15H24 4.14Trans-γ-bisabolene C15H24 5.43ent-pimara-8(14),15-diene C20H32 2.49

Discussion

Chemical compound Formula %Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydro-1,1,4a,7-tetramethyl-, [4aS-(4aα,4bβ,7β,10aβ)]-

C20H32 4.95

Isomaturnin C16H14O3 3.12

Phenanthrene, 7-ethenyl-1,2,3,4,4a,4b,5,6,7,8,10,10a-dodecahydro-1,1,4a,7-tetramethyl-, [4aS-(4aα,4bβ,7β,10aβ)]-Isomaturnin C16H14O3 3.1210,11-Dihydrobenzo[k]fluoranthene C20H14 3.08Acetamide, N-[4-(trimethylsilyl)phenyl]- C11H17NOSi 8.35Retinol C20H30O 25.32Methyl 3-bromo-1-adamantaneacetate C13H19BrO2 18.18p-Trimethylsiloxybenzaldehyde oxime, trimethylsilyl- C13H23NO2Si2 4.59Propiophenone, 2'-(trimethylsiloxy)- C12H18O2Si 2.29

• Chemical compounds yielded from dammar resin aredifferent with four various solvents, however, there is noone of those four solvents could detect all containedchemical compounds from other solvent. Therefore, allthese four solvents must be applied to detect all thecontained chemical compounds of dammar resin.

• Based on the reading results of GC-MS, we obtainedthat hydrocarbon chains contained in dammar resin arepotential to be used as fuel, and various bond carbon indammar resin increasing the promising potential ofdammar resin as a good source of fuel energy.

Discussion

• Chemical compounds yielded from dammar resin aredifferent with four various solvents, however, there is noone of those four solvents could detect all containedchemical compounds from other solvent. Therefore, allthese four solvents must be applied to detect all thecontained chemical compounds of dammar resin.

• Based on the reading results of GC-MS, we obtainedthat hydrocarbon chains contained in dammar resin arepotential to be used as fuel, and various bond carbon indammar resin increasing the promising potential ofdammar resin as a good source of fuel energy.

Conclusions

• Using GC-MS method, CHCl3 and C6H14 solvents givingsimilar graph and the detected chemical compound arerelatively similar. Using CH3COOH and CH3OH alsogiving the similar results. The significant different resultsare given by other solvents besides those two previouscouple solvents mentioned above.

• Using GC-MS method, it was detected about 32 and 25chemical compounds when using CHCl3 and C6H14respectively. Meanwhile, there were 17 and 15 chemicalcompounds detected when using CH3COOH andCH3OH respectively.

• Using GC-MS method, CHCl3 and C6H14 solvents givingsimilar graph and the detected chemical compound arerelatively similar. Using CH3COOH and CH3OH alsogiving the similar results. The significant different resultsare given by other solvents besides those two previouscouple solvents mentioned above.

• Using GC-MS method, it was detected about 32 and 25chemical compounds when using CHCl3 and C6H14respectively. Meanwhile, there were 17 and 15 chemicalcompounds detected when using CH3COOH andCH3OH respectively.

• All these solvents giving different results, however, theresults are complementing each other because there isa solvent that could detect a chemical compound whereother solvents could not detect that chemicalcompound.

• Based on chemical compounds contained in dammarresin, it can be concluded that dammar resin has apromising potency to be used as alternative renewablefuel energy.

Conclusions

• All these solvents giving different results, however, theresults are complementing each other because there isa solvent that could detect a chemical compound whereother solvents could not detect that chemicalcompound.

• Based on chemical compounds contained in dammarresin, it can be concluded that dammar resin has apromising potency to be used as alternative renewablefuel energy.

Jamal

Mechanical Engineering Department