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DOI: 10.1039/C6RA24200F
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13X 1/16) in the drybox. Methyl oleate (≥ 99%), cisꢀstilbene, βꢀ the gas chromatograph with FID detector (GCꢀFID) and the gas
pinene, cisꢀ4ꢀoctene, cisꢀ1,4ꢀdiacetoxyꢀ2ꢀbutene, chromatograph mass spectrometer (GC/MS). The results of
vanillideneacetone, allyl trimethylsilane and allyl glycidal ether crossꢀmetathesis reactions are summarised in Table 2ꢀ3.
were used in the drybox as received (Aldrich Chemical Co. or
Tokyo Chemical Industry Co., lLtd.) without purification.
Acknowledgements
Grubbs catalyst 1st generation RuCl2(PCy3)2(CHPh) (
generation RuCl2(PCy3)(H2IMes)(CHPh) ( ) and Hoveydaꢀ
Grubbs catalyst 2nd generation RuCl2(IMesH2)(CHꢀ2ꢀOiPrꢀ
C6H4) ( ) were used in the drybox as received [Cy =
cyclohexyl, IMesH2 1,3ꢀbis(2,4,6ꢀ
1), 2nd
2
W.A. acknowledges to Tokyo Metropolitan University (TMU),
Tokyo Metropolitan government (Asian Human Resources
Fund) for a fellowship of coꢀtutorial program between TMU
3
=
and Universiti Kebangsaan Malaysia (UKM).
We also
trimethylphenyl)imidazolinꢀ2ꢀylidene] (Aldrich Chemical Co.).
Nonane and dodecane purchased from Tokyo Chemical
Industry Co., Ltd were used as the internal standard (IS) for GC
analyses.
The gas chromatograph mass spectrometer (GC/MS) analyses
were performed on Shimadzu GCꢀ17A gas chromatograph
directly coupled to the mass spectrometer system (MS) of
Shimadzu GCMS QP5050. Agilent column model DBꢀ1 30m
length, 0.25mm in diameter and film thickness and
polyethylene glycol stationary phase was used throughout the
experiment. Helium was used as the carrier gas at a flow rate of
1.7 mL/min.
appreciate a partial support from UKM for a preliminary study
at UKM (FRGS/2/2014/ST01/UKM/1). B.H. expresses her
thanks to IAESTE (The International Association for the
Exchange of Students for Technical Experience) for the
internship program. The project was partly supported by an
international joint research program (sponsored by TMU) and
the advanced research program (Tokyo Metropolitan
government). Authors express their thanks to Profs. S. Komiya
and A. Inagaki (TMU) for discussions.
Notes and references
Shimadzu GCꢀ2025 gas chromatograph with FID detector (GCꢀ
FID) was employed for quantitative analysis of the starting
materials and products using a (0.25 ꢁm x 0.25 mm x 30m)
DBꢀ1 column. Nitrogen gas was used as the carrier gas at a
flow rate of 2.0 mL/min. The quantitative analyses were
performed by comparing the peak area of the products with
known amount of nonane or dodecane as an internal standard.
Calibration coefficient was determined by analyzing the
mixtures of MO and the internal standard with different ratios.
The amount of MO was calculated by normalization using the
internal standard method with the calibration coefficient. The
conversion of MO was obtained from the comparison of peak
areas before and after reactions.
1
For example, (
WileyꢀVCH: Weinheim, Germany, 2003; (
Olefin Metathesis: Theory and Practice; John Wiley & Sons,
Inc. Hoboken, New Jersey, USA, 2014; ( ) R. H. Grubbs and
A. G. Wenzel, Eds. Handbook of Metathesis 2nd Ed.; Vol. 1,
WileyꢀVCH: Weinheim, Germany, 2015.
a
) R. H. Grubbs, Ed. Handbook of Metathesis
;
b) K. Grela, Ed.
c
2
For example, (
39, 3012; ( ) T. M. Trnka and R. H. Grubbs, Acc. Chem. Res.,
2001, 34, 18; ( ) R. R. Schrock and A. H. Hoveyda, Angew.
Chem. Int. Ed., 2003, 42, 4592; ( ) A. K. Chatterjee, In
Handbook of Metathesis; R. H. Grubbs, Ed.; WileyꢀVCH:
Weinheim, Germany, 2003; Vol. 2, p.246; C.
Samojzowicz, M. Bieniek and K. Grela, Chem. Rev. 2009,
109, 3708; ( ) G. Vougioukalakis and R. H. Grubbs, Chem.
a) A. Fürstner, Angew. Chem. Int. Ed., 2000,
b
c
d
(e)
f
Rev., 2010, 110, 1746; (
Rev., 2009, 109, 3783.
g) S. Monfette and D. Fogg, Chem.
Self-metathesis reaction of methyl oleate (MO). Typical
procedure (run 2, Table 1) is as follows. Methyl oleate (MO,
0.593 g, 2.00 mmol) and dodecane (0.100 g) as an internal
standard for GC analyses were dissolved in 1.0 mL of CH2Cl2
3
(
a
) U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O.
Metzger and H. J. Schäfer, Angew. Chem. Int. Ed., 2011, 50,
3854; ( ) L. M. de Espinosa and M. A. R. Meier, In
b
Organometallics and Renewables; M. A. R. Meier, B. M.
Weckjusen and P. C. A. Bruijnincx, Eds.; Springer-Verlag,
(DCM).
Grubbs
catalyst
2nd
generation
Berlin Heidelberg, Germany, 2012; p.1; (c) A. Nickel and R.
L. Pederson, In Olefin Metathesis: Theory and Practice; K.
Grela, Ed.; John Wiley & Sons, Inc. Hoboken, New Jersey,
USA, 2014; p. 335; (d) J. H. Philips, In Handbook of
Metathesis 2nd Ed.; R. H. Grubbs, A. G. Wenzel, D. J.
O'Leary and E. Khosravi, Eds.; WileyꢀVCH: Weinheim,
Germany, 2015; Vol. 3, p.357; (e) M. A. R. Meier, Macromol.
Chem. Phys., 2009, 210, 1073.
For examples (Jatropha bioꢀdiesel production and use), W. M.
J. Achten, L. Verchot, Y. J. Franken, E. Mathijs, V. P. Singh,
R. Aerts and B. Muys, Biomass and Bioenergy, 2008, 32,
1063.
Self metathesis and ethenolysis of unsaturated fatty acid
esters (exemplified by methyl oleate, MO), (a) K. A. Burdett,
L. D. Harris, P. Margl, B. R. Maughon, T. MokhtarꢀZadeh, P.
C. Saucier and E. P. Wasserman, Organometallics, 2004, 23,
2027; (b) G. S. Forman, A. E. McConnell, M. J. Hanton, A.
RuCl2(PCy3)(H2IMes)(CHPh) (
2
) (0.0085 g, 0.5 mol%, 0.010
mmol) was added into the solution. The mixture was stirred at
50 ºC for 1 hour, and then the resulting mixture was filtered
through a Celite pad. The obtained filtrate was analyzed using
the gas chromatograph with FID detector (GCꢀFID) and the gas
chromatograph mass spectrometer (GC/MS). The results of
selfꢀmetathesis reactions are summarised in Table 1.
Cross-metathesis reaction of methyl oleate (MO) with
olefins. Typical procedure (run 11, Table 2) is as follows.
Methyl oleate (MO, 0.593 g, 2.00 mmol), cisꢀ4ꢀoctene (CO,
0.224g, 2.00 mmol) and nonane (0.100 g) as an internal
standard for GC analyses were dissolved in 1.0 mL of CH2Cl2
4
5
(DCM).
Grubbs
catalyst
2nd
generation
RuCl2(PCy3)(H2IMes)(CHPh) (
2) (0.0085 g, 0.5 mol%, 0.010
M. Z. Slawin, R. P.Tooze, W. J. van Rensburg, W. H. Meyer,
C. Dwyer, M. M. Kirk and D. W. Serfontein,
mmol) was added into the solution. The mixture was stirred at
50 ºC for 1 hour, and then the resulting mixture was filtered
through a Celite pad. The obtained filtrate was analyzed using
Organometallics, 2004, 23, 4824;
(c) C. Thurier, C.
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