PROS Ilmimada H, Edi Priyo U, Warsito Oxidation against fulltext
Proceedings of the IConSSE FSM SWCU (2015), pp. BC.61–63
BC.61
ISBN: 978-602-1047-21-7
Oxidation against to -guaiene at various time of aeration
Ilmimada Harfiya*, Edi Priyo Utomo, Warsito
a
Department of Chemistry, Brawijaya University. Jl. Veteran Malang, 65145 Indonesia
Email: *harfiya.ilmimada@yahoo.com
Abstract
Deuterium-labeled guaiane derivatives and the precursors, namely -guaiene, was
synthesized in good yields as GC-MS internal standards for comparing the behavior of guaiene autoxidative conditions. It was found that approximately 99% of -guaiene
poured into vial bottle and added water then flowed oxygen at ambient temperature
was autoxidized after 6 days and up to 35% of rotundone was formed during this period.
The results indicate the feasibility of rapid changes of aroma profiles of herbs and other
plant materials over time when exposed to air.
Keywords
1.
-guaiene, autoxidation, rotundone
Introduction
Sesquiterpenes are an important aroma source and have long been used as fragrances
in the perfumery and cosmetic industries (Ansari & Curtis, 1974). Patchouli oil is an important
raw material for the perfume and cosmetics industries, besides being used as a natural
additive for food flavoring. -guaiene is the second main component after patchouli alcohol
in patchouli oil (Sundaresan et al., 2009).
Transformation of -guaiene into fine chemicals by oxidation reaction was also
reported by other researcher. It applied various different oxidation times. Oxidation using guaiene coated onto filter paper and exposed to air at ambient temperature was autoxidized
(Huang et al., 2015). This result will be reported oxidation of -guaiene using pure oxidation.
2.
Materials and methods
The materials used for research including -guaiene oil 96% from patchuoli oil. Other
materials were some chemicals used as bought from the manufacturer or as mentioned,
including pure oxygen, ethyl acetate, magnesium sulfate anhydrate (Merck), and aquadest.
0.1 g guaiene oil poured into vial bottle and 10 mL aquadest, and then the mixture was
aerated with oxigen at flow rate 90 mL/minute. The aeration was varied at various time. After
aeration, the mixture was partitioned with 30 mL ethyl acetate. Organic phase was separated
and dried under magnesium sulfate anhydrate. The product was monitored by GCMSQP2010S, completed with column RTX-MSS, sample was injected at 1 µL, at 250oC for port
injector, and 5 mL/min for He gas flowrate.
3.
Results and discussion
Oxidation of -guaiene uses simple aerial oxidation condition, as reported by Huang et
al. (2015), provided up to 7% of rotundone. Reaction was undertaken at room temperature
for 6 days. Investigation of oxidation guaiene uses water condition. Product is determined by
using gas chromatography-mass spectrometry provided a chromatogram.
SWUP
Oxidation against to α -guaiene at various time of aeration
BC.62
Figure 1. Chromatogram of standard -guaiene.
Figure 2. Chromatogram of oxidation reaction product of guaiene.
Peak
number
1
2
Table 1. Tabulation of standard -guaiene.
tR (min)
14.956
15.106
Area (%)
Compounds
MW (SI)
942578
122436867
Trans-caryophyllene
-guaiene
204(88)
204(95)
Table 2. Tabulation of the oxidation reaction product of -guaiene.
Peak
tR (min)
Area (%)
Compounds
MW (SI)
number
1
15.041
7798481
-guaiene
204 (89)
2
15.967
18839469 (-)-Caryophyllene oxide
220 (86)
3
16.679
1872429 Unknown
224 (85)
4
17.308
2153497 patchulane
220 (85)
5
17.746
2934267 Unknown
332 (84)
6
17.992
1690380 Trans-Caryophyllene
218 (86)
7
19.006
1155837 LIMONENEDIOXIDE 1
168 (86)
8
19.348
1908479 Unknown
208 (85)
9
19.581
2593360 Unknown
208 (84)
10
19.755
12889445 3-rotundone
218 (92)
*
Note: The compounds was characterized from library of the GC-MS with wiley
7 as reference.
Standard -guaiene oil was monitored by GCMS-QP2010S, completed with column
RTX-MSS, sample was injected at 1 µL, at 250oC for port injector, and 5 mL/min for He gas
flowrate. provided shown on Figure 1. In general, it was found two compounds detected,
that are -guaiene and trans-caryohyllene.
SWUP
I. Harfiya, E.P. Utomo, Warsito
BC.63
The product of oxidation againts to -guaiene at 6 days was monitored by GCMSQP2010S, completed with column RTX-MSS, sample was injected at 1 µL, at 250oC for port
injector, and 5 mL/min for He gas flowrate. provided shown on Figure 2. In general, it was
found 10 compounds detected, the product of oxidation still detected -guaiene at retention
time (tR) 15.041 min. The novel product was found at retention time (tp) 19.755 min with
molecular weight 218 and SI 92.
4. Conclusion and remarks
Guaiene oxidation were done by various time. It was found that approximately 96% guaiene aerated by pure oxigen at air ambient temperature after 124 h and up to 15% of
rotundone was formed during this period.
References
Ansari, H., & Curtis, A., (1974) Sesquiterpenes in the perfumery industry. J. Soc. Cosmet. Chem., 25,
203 231.
Huang, A.-C., Sefton, M.A., & Taylor, D.K. (2015). Comparison of the formation of peppery and woody
sesquiterpenes derived from -guaiene and -bulnesene under aerial oxidative conditions.
Journal of Agricultural and Food Chemistry, 63, 1932 1938.
Sundaresan, V., Singh, S.P., & Mishra, A.N. (2009). Composition and comparison of essential oils of
Pogestemon Cablin (Blanco) Bent. (Patchouli) and Pogostemon travancoricus Bedd. var.
travaancoricus. Journal of Essential Oil Research, 21(3), 220 222.
SWUP
BC.61
ISBN: 978-602-1047-21-7
Oxidation against to -guaiene at various time of aeration
Ilmimada Harfiya*, Edi Priyo Utomo, Warsito
a
Department of Chemistry, Brawijaya University. Jl. Veteran Malang, 65145 Indonesia
Email: *harfiya.ilmimada@yahoo.com
Abstract
Deuterium-labeled guaiane derivatives and the precursors, namely -guaiene, was
synthesized in good yields as GC-MS internal standards for comparing the behavior of guaiene autoxidative conditions. It was found that approximately 99% of -guaiene
poured into vial bottle and added water then flowed oxygen at ambient temperature
was autoxidized after 6 days and up to 35% of rotundone was formed during this period.
The results indicate the feasibility of rapid changes of aroma profiles of herbs and other
plant materials over time when exposed to air.
Keywords
1.
-guaiene, autoxidation, rotundone
Introduction
Sesquiterpenes are an important aroma source and have long been used as fragrances
in the perfumery and cosmetic industries (Ansari & Curtis, 1974). Patchouli oil is an important
raw material for the perfume and cosmetics industries, besides being used as a natural
additive for food flavoring. -guaiene is the second main component after patchouli alcohol
in patchouli oil (Sundaresan et al., 2009).
Transformation of -guaiene into fine chemicals by oxidation reaction was also
reported by other researcher. It applied various different oxidation times. Oxidation using guaiene coated onto filter paper and exposed to air at ambient temperature was autoxidized
(Huang et al., 2015). This result will be reported oxidation of -guaiene using pure oxidation.
2.
Materials and methods
The materials used for research including -guaiene oil 96% from patchuoli oil. Other
materials were some chemicals used as bought from the manufacturer or as mentioned,
including pure oxygen, ethyl acetate, magnesium sulfate anhydrate (Merck), and aquadest.
0.1 g guaiene oil poured into vial bottle and 10 mL aquadest, and then the mixture was
aerated with oxigen at flow rate 90 mL/minute. The aeration was varied at various time. After
aeration, the mixture was partitioned with 30 mL ethyl acetate. Organic phase was separated
and dried under magnesium sulfate anhydrate. The product was monitored by GCMSQP2010S, completed with column RTX-MSS, sample was injected at 1 µL, at 250oC for port
injector, and 5 mL/min for He gas flowrate.
3.
Results and discussion
Oxidation of -guaiene uses simple aerial oxidation condition, as reported by Huang et
al. (2015), provided up to 7% of rotundone. Reaction was undertaken at room temperature
for 6 days. Investigation of oxidation guaiene uses water condition. Product is determined by
using gas chromatography-mass spectrometry provided a chromatogram.
SWUP
Oxidation against to α -guaiene at various time of aeration
BC.62
Figure 1. Chromatogram of standard -guaiene.
Figure 2. Chromatogram of oxidation reaction product of guaiene.
Peak
number
1
2
Table 1. Tabulation of standard -guaiene.
tR (min)
14.956
15.106
Area (%)
Compounds
MW (SI)
942578
122436867
Trans-caryophyllene
-guaiene
204(88)
204(95)
Table 2. Tabulation of the oxidation reaction product of -guaiene.
Peak
tR (min)
Area (%)
Compounds
MW (SI)
number
1
15.041
7798481
-guaiene
204 (89)
2
15.967
18839469 (-)-Caryophyllene oxide
220 (86)
3
16.679
1872429 Unknown
224 (85)
4
17.308
2153497 patchulane
220 (85)
5
17.746
2934267 Unknown
332 (84)
6
17.992
1690380 Trans-Caryophyllene
218 (86)
7
19.006
1155837 LIMONENEDIOXIDE 1
168 (86)
8
19.348
1908479 Unknown
208 (85)
9
19.581
2593360 Unknown
208 (84)
10
19.755
12889445 3-rotundone
218 (92)
*
Note: The compounds was characterized from library of the GC-MS with wiley
7 as reference.
Standard -guaiene oil was monitored by GCMS-QP2010S, completed with column
RTX-MSS, sample was injected at 1 µL, at 250oC for port injector, and 5 mL/min for He gas
flowrate. provided shown on Figure 1. In general, it was found two compounds detected,
that are -guaiene and trans-caryohyllene.
SWUP
I. Harfiya, E.P. Utomo, Warsito
BC.63
The product of oxidation againts to -guaiene at 6 days was monitored by GCMSQP2010S, completed with column RTX-MSS, sample was injected at 1 µL, at 250oC for port
injector, and 5 mL/min for He gas flowrate. provided shown on Figure 2. In general, it was
found 10 compounds detected, the product of oxidation still detected -guaiene at retention
time (tR) 15.041 min. The novel product was found at retention time (tp) 19.755 min with
molecular weight 218 and SI 92.
4. Conclusion and remarks
Guaiene oxidation were done by various time. It was found that approximately 96% guaiene aerated by pure oxigen at air ambient temperature after 124 h and up to 15% of
rotundone was formed during this period.
References
Ansari, H., & Curtis, A., (1974) Sesquiterpenes in the perfumery industry. J. Soc. Cosmet. Chem., 25,
203 231.
Huang, A.-C., Sefton, M.A., & Taylor, D.K. (2015). Comparison of the formation of peppery and woody
sesquiterpenes derived from -guaiene and -bulnesene under aerial oxidative conditions.
Journal of Agricultural and Food Chemistry, 63, 1932 1938.
Sundaresan, V., Singh, S.P., & Mishra, A.N. (2009). Composition and comparison of essential oils of
Pogestemon Cablin (Blanco) Bent. (Patchouli) and Pogostemon travancoricus Bedd. var.
travaancoricus. Journal of Essential Oil Research, 21(3), 220 222.
SWUP