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S1
Microalgae Lipids as a Feedstock for Production of Benzene
Dennis Pingen, Julia Zimmerer, Nele Klinkenberg, Stefan Mecking*
Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Germany
Supporting Information
Additional Experimental Procedures and Results S2
Gas Chromatography S6
NMR spectra S21
References S22
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2018
S2
Additional Experimental Procedures and Results
Procedure for the hydrogenation of a model metathesis mixture
A mixture of 4-octene (2.5 mmol), oleic acid (5 mmol) and 1,18-octadecenedioic acid (2.5 mmol) was prepared. This resembles the metathesis of EPA mixture without 1,4-cyclohexadiene present. The mixture was dissolved in degassed toluene. In a glass inlet for autoclaves, Pd/C (53.2 mg, 10% w/w) and a stirring bar were placed. The glass inlet was placed in the autoclaved with was subsequently closed. The autoclave was purged with nitrogen. The solution of the model metathesis mixture was transferred to the autoclave. After pressurization with H2 (5 bar) the autoclave was placed into a preheated aluminium block and allowed to stir for 8 hours at 110°C. Samples were taken at t=0, 15, 30, 60, 120, 240, 360, 480 minutes. All samples where measured by GC and were esterified using methanol prior to the measurement.
Table S1: Results in the subsequent one-pot metathesis and dehydrogenation of eicosapentaenoic acid.
Entry Dehydrogenation cat. (loading)
Temp. (°C)
Notes Time (h) Conversion of 1,4-cyclohexadiene (%)a,b
Benzene Selectivity (%)a,b
1c,d Pd/C (5 mol%) 110 1 equiv. fumarate, 1,4-cyclohexadiene isolated from EPA metathesis
20 100 66
2 Pd/Al2O3 (0.1 mol%)
70 Isolated conjugated EPA
6 0 0
3 Pd/Al2O3 (0.1 mol%)
70 20 0 0
4 Pd/Al2O3 (0.1 mol%)
90 Mixture of entry 3
20 0 0
5 Pd/Al2O3 (0.1 mol%)
110 Mixture of entry 4
20 100 33
6 -- 45110 No Pd cat 0.25+20 100 0Conditions: HGII (0.005 mmol, 0.1 mol%), 10 mL toluene, 45°C, 15 min. after this, Pd, was added a) Analysed by GC, the conversion of the metathesis was determined with respect to the consumption of EPA. 1,4-Cyclohexadiene selectivity is determined with respect to EPA. b) The benzene conversion and selectivity was based on EPA. c) 0.2 equiv. AMS added as hydrogen accepted. d) Chlorobenzene instead of toluene as a solvent.
S3
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.00
10
20
30
40
50
60
70
80
90
100C
ompo
sitio
n [%
]
Time [h]
Graph S1: Reaction profile of the dehydrogenation of 1,4-cyclohexadiene over 0.1 mol% Pd/Al2O3 (5%w/w) at 110°C. Conditions: 1,4-cyclohexadiene (10 mmol), Pd/Al2O3(5%) (0.01 mmol, 0.1 mol%), toluene (10 mL), 110°C, 4h. ■= 1,4-cyclohexadiene, ●= 1,3-cyclohexadiene, ▲= cyclohexene, ▼= benzene.
The selectivity to 1,4-cyclohexadiene was determined over the conversion of EPA, that is a ratio of benzene formed to EPA consumed of 2:1 corresponds to 100% selectivity.
Additionally, the dehydrogenation of neat 1,4-cyclohexadiene was investigated to determine the conditions required for the subsequent dehydrogenation of the metathesis reaction mixture.[, 1,2] Upon dehydrogenation of 1,4-cyclohexadiene, hydrogen is liberated from the molecule, therefore it is possible that a hydrogen acceptor is required to prevent that the hydrogen can hydrogenate 1,4-cyclohexadiene in the mixture.[3] A procedure reported for the dehydrogenation of cyclohexene was adopted initially, where various Pd sources and AMS (Anthraquinone-2-sulfonic acid sodium salt) as hydrogen transfer agent are used. Generally the dehydrogenation of cyclohexene or cyclohexadienes to benzene proceeds at high temperatures, and the use of a hydrogen acceptor and transfer agent may allow to work at lower temperatures. A known procedure employing these conditions is actually used in the aerobic oxidation of cyclohexene to benzene, where oxygen is the hydrogen acceptor and facilitates the reaction due to water formation.[4,5] An olefin was chosen here as hydrogen acceptor to investigate if the remaining olefins of the EPA metathesis can be used as hydrogen acceptor later in a one-pot reaction. The results of the dehydrogenation screening are listed in Figure S1.
S4
0
10
20
30
40
50
60
70
80
90
100
Pd/C
Pd/C
Pd/C
5 mol
% f
Pd/C
Pd/C
Pd/C
Pd/C
0.1 m
ol%
f
0.1 m
ol%
f
1 mol
% f
1 mol
% f
5 mol
% b
5 mol
% b
,c
5 mol
% b
,c,d
5 mol
% b
,c,e
5 mol
% b
,c,d
Pd/A
l 2O 3
Pd/A
l 2O 3
5 mol
% b
,c,e
Pd(O
Ac) 2
Sele
ctiv
ity (%
)
Catalyst (mol%)
Benzene Cyclohexene
Pd(O
Ac) 2
Figure S1: Results of the dehydrogenation of 1,4-cyclohexadiene employing different Pd catalysts under different conditions. Conditions: 1,4-cyclohexadiene (10 mmol), Pd catalyst (0.5 mmol (5 mol%) or 0.001 mmol (0.1 mol%), solvent (10 mL), 20h, 110°C. a) Analysed by GC., conversion was complete in all cases. b) In chlorobenzene as a solvent (10mL) c) 0.2 equivalents AMS were added. d) 1 equivalent dimethyl fumarate was added. e) 0.25 equivalent dimethyl fumarate was added. f) In toluene as a solvent.
Under the reaction conditions as described for aerobic cyclohexene oxidation, the 1,4-cyclohexadiene readily reacts to benzene over Pd(OAc)2 as a catalyst with a small amount of by-product, which was identified as cyclohexene (Figure S1, column 1). Most remarkably, only about 25% of the dimethyl fumarate was hydrogenated to dimethyl succinate. For this reason, the amount of dimethyl fumerate was reduced to only 25%. Notable, the selectivity towards benzene was now only 50%, giving a strong indication that the fumarate still does have a function (Figure S1, column 2). Cyclohexene was present in much higher amount now (1:1 ratio), which is the result of 1,4-cyclohexadiene hydrogenation. The catalyst range was expanded to supported Pd catalysts for further optimization. With both Pd/Al2O3 and Pd/C full conversion was achieved.[6] The same conditions were employed and benzene was formed in 95% selectivity, only slightly higher compared to Pd(OAc)2. Surprisingly, in the case where dimethyl fumerate was employed as a hydrogen acceptor, the amount of hydrogenated dimethyl succinate was minimal (column 4 and 5, Figure S1), and therefore any hydrogen acceptor and AMS were further omitted. Notably, full conversion was achieved, without the presence of a hydrogen acceptor in employing supported Pd catalysts. The selectivity towards benzene was in both cases 100% (column 6 and 7, Figure S1). The catalyst loading was reduced to 1 mol% and to 0.1 mol%. With both loadings, full conversion is achieved, though with 1 mol% also full selectivity to benzene was achieved, whereas only 65% selectivity was reached with 0.1 mol% catalyst loading (column 8-11, Figure S1). Cyclohexene was again observed as a side product (column 11, Figure S1). To learn more about the reaction and all the intermediates, reaction profiles were recorded by taking samples at specified time-intervals. The system using Pd/Al2O3 as a catalyst was chosen as this gave a good conversion, but still showed the side products in sufficient amount for analysis. A loading of 0.1 mol% was chosen to observe intermediates and possible side products optimally (Graph S2)Graph S1.
S5
0 1 2 3 4 5 6 7 8 9 10 11 120
20
40
60
80
100C
ompo
sitio
n [%
]
Time [h]1 2 3 4 5 6 7 8 9 10 11 12
0
10
20
30
40
50
60
70
80
90
100
Com
posi
tion
[%]
Time [h]
Graph S2: Reaction profile of the dehydrogenation of 1,4-cyclohexadiene over 0.1 mol% Pd/Al2O3 (5%w/w) at 70°C. Conditions: 1,4-cyclohexadiene (10 mmol), Pd/Al2O3(5%) (0.01 mmol, 0.1 mol%), toluene (10 mL left, 1 mL right), 70°C, 12h. ■= 1,4-cyclohexadiene, ●= 1,3-cyclohexadiene, ▲= cyclohexene, ▼= benzene.
The reaction was first performed at 110°C which already showed 25% conversion during heating up (t = 0 in Graph S1Graph S2). For better observation of intermediates, the temperature was reduced to 70°C. It can be seen that complete conversion is achieved in about 1 hour (Graph S2). Here it becomes obvious that the 1,4-cyclohexadiene is indeed converted into benzene, though via an intermediate. First cyclohexene is formed, with at the same time one equivalent of benzene.[7] The hydrogen from the dehydrogenated 1,4-cyclohexadiene is first transferred to a second 1,4-cyclohexadiene molecule. Over time, the cyclohexene is further converted to benzene, which must proceed over a loss of two hydrogen equivalents. The latter reaction appeared to be much slower, though still viable under these conditions, and therefore the concentration of the compounds in the reaction mixture was increased, by reduction of the solvent volume (Graph S2, right). The dehydrogenation of both 1,4-cyclohexadiene and cyclohexene is now indeed slightly increased.
0 50 100 150 200 250 300 350 400 4500
10
20
30
40
50
60
70
80
90
100
Con
vers
ion
(%)
Time (min)
4-octene oleic acid 1,18-diacid
Graph S3: Reaction profile of the hydrogenation of a model metathesis-mixture of 4-octene, oleic acid and 1,18-octadecenedioic acid. Conditions: 4-octene (2.5 mmol, 392 µL), oleic acid (5 mmol, 1.6 mL), 1,18-octadecenedioic acid (2.5 mmol, 781 mg), toluene (10 ml), Pd/C (53.2 mg), 110°C, 8 h.
Form the above graph (Graph S3), it can be seen that oleic acid hydrogenation reaches full conversion slower than 4-octene or the diacid. As this is a model for the metathesis mixture, it can be expected that the same occurs in the hydrogenation of the post-metathesis mixture. As was observed in this,
S6
the equilibrium seemed to have shifted towards the diacid. This is now supported by the difference in hydrogenation rate of all components.
Gas Chromatography
Gas chromatography was measured on a Perkin-Elmer GC Clarus 500 equipped with an elite-5 column (Length = 30 m, Inner Diameter = 0.25 mm, Thickness = 25 µ) and a FID-detector via the following programs: 1 min at 90°C, 30°C/min to 280°C, 280°C for 8 minutes (method 1), or 3 min at 50°C, 20°C/min to 280°C, 280°C for 5 minutes (method 2), both with an injector temperature of 300°C and a detector temperature of 280°C.
Table S2: Retention times of the compounds detected from the metathesis of EPA and the dehydrogenation reactions. Response factors were measured with respect to dodecane.
Component Method 1 Method 2 Molar Response factor1,3-cyclohexadiene -- 2.32 0.49Cyclohexane 1.66 2.42 0.51Benzene 1.67 2.46 0.50Cyclohexene 1.69 2.61 0.491,4-cyclohexadiene 1.77 2.92 0.49Methyl 5-octenoate 3.42 7.67-7.76 *dodecadiene 3.85 8.31 *Methyl 5,8-undecadienoate 4.82 9.78 *Dimethyl decenedioate 5.70 10.93-11.11 0.91Methyl tetradecatrienoate 6.00 11.54 *Octadecapentaene 6.25 -- *EPA 7.86 14.31 1.70
* Estimated using comparable compounds
S7
2 3 4 5 6 7 8 9 10 11 12 13 14 150.00.51.01.52.02.53.03.54.04.55.05.56.06.5
solid after evaporation metathesis mixture
EPA self-meta-thesis mixture
1,4-cyclohexadiene
dimethyl decanedioate
methyl octanoate
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
EPA
Figure S2: GC traces (method 2) of the metathesis of EPA with pure compounds for comparison. Methyl octanoate was used for comparison to methyl octenoate. Dimethyl decanedioate was used for comparison of dimethyl decenedioate because of the very similar retention times (Vide Inra, Figure S4).
3.30 3.35 3.40 3.45 3.50 3.55 3.6002468
101214161820
EPA metathesis mixture -hydrogenated methyloctanoate enriched
EPA metathesis mixture -hydrogenated
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
EPA metathesis mixture
Figure S3: GC traces (method 1) of the reaction mixture from incomplete EPA metathesis, which was subsequently hydrogenated and enriched with methyl octanoate (8:0 ester). The retention time of the saturated and unsaturated compound are very similar, though these differ sufficiently to distinguish both components.
S8
4.75 4.80 4.85 4.90
0
2
4
6
8
10
12
EPA metathesis mixture -hydrogenated dimethyldecanedioate enriched
EPA metathesis mixture -hydrogenatedN
orm
aliz
ed In
tens
ity (a
.u.)
Retention Time (min)
EPA metathesis mixture
Figure S4: GC traces (method 1) of the reaction mixture from incomplete EPA metathesis mixture, which was subsequently hydrogenated and enriched with dimethyl decanedioate (1:10 diester). The retention time of the saturated and unsaturated compound are very similar, though these differ sufficiently to distinguish both components.
Table S3: Areas of the remaining by-products from a dried metathesis sample measured by GC using method 2.
Signal Compound Area (%)a
7.67-7.76 Methyl 5-octenoate
60
10.93-11.11 Dimethyl decenedioate
11
9.78 Methyl 5,8-undecadienoate
29
a) The ratio between methyl 5-octenoate and dimethyl 5-decenedioate is as expected; 2:1.
Figure S5: GC-trace (method 2) of a post-metathesis mixture of EPA after evaporation of all volatile compounds.
2 4 6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
methyl 5,8-undecadienoate
dimethyl 5-decenedioate
Nor
mal
ized
inte
nsity
(a.u
.)
Retention Time (min)
methyl 5-octenoate
S9
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
0
2
4
6
8
10
incomplete dehydrogenation in toluene
CHD dehydrogenation in chlorobenzene
CHD dehydrogenation in toluene
1,3-cyclohexadiene
1,4-cyclohexadiene
benzene
cyclohexene
cyclohexane
toluene
Nor
mal
ized
Inte
nsiti
es (a
.u.)
Retention Time (min)
chlorobenzene
Figure S6: GC traces (method 2) of dehydrogenation reactions in chlorobenzene and toluene and the pure compounds for comparison.
2 3 4 5 6 7 8
0.00.51.01.52.02.53.03.54.04.55.05.5
dehydrogenation in the presence of dimethylfumarate
benzene
cyclohexene
dimethyl fumarate
Nor
mal
ized
Inte
nsiti
es (a
.u.)
Retention Time (min)
dimethyl succinate
Figure S7: GC traces (method 2) of a 1,4-cyclohexadiene dehydrogenation reaction mixture in the presence of dimethyl fumarate. The GC traces of pure compounds have been added for comparison.
S10
2.0 2.5 3.0 3.5 4.00.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.2
reaction mixture
enriched with benzene
Nor
mal
ized
Inte
nsiti
es (a
.u.)
Retention Time (min)
enriched with benzene and cyclohexene
Figure S8: GC traces (method 2) of a representative reaction mixture of the dehydrogenation of 1,4-cyclohexadiene (bottom) enriched with benzene (centre) and cyclohexene (top).
2 3 4 5 6 7 8 9 10 11 12
0.0
0.2
0.4
0.6
0.8
1.0
45
3
1
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
2
Figure S9: Exemplary GC trace (method 2) of a the metathesis reaction mixture of EPA followed directly by the dehydrogenation of 1,4-cyclohexadiene. In this case also incomplete conversion is shown, with cyclohexene as by-product. Compounds: 1: benzene, 2: cyclohexene, 3: methyl 5-octenoate, 4: dimethyl 5-decenedioate, 5: methyl 5,8-undeceneoate.
S11
EPA metathesis EPA metathesis and dehydrogenation methyl octanoate
7.40 7.45 7.50 7.55 7.60 7.65 7.70 7.75 7.80 7.85 7.900.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1N
orm
aliz
ed In
tens
ity (a
.u.)
Retention time (min)Figure S10: Detail of Figure S9 in the methyl 5-octenoate region, with a comparison to pure methyl octanoate to emphasize that no hydrogenation occurs (method 2).
EPA metathesis dimethyl decanedioate EPA metathesis and dehydrogenation
11.00 11.05 11.10 11.15 11.20 11.250.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention time (min)Figure S11: Detail of Figure S9 in the dimethyl decanedioate region, with a comparison to pure dimethyl decanedioate to emphasize that no hydrogenation occurs.
S12
2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0
0.0
0.2
0.4
0.6
0.8
benzene:1,3-cyclohexadiene - 1:1
benzene:1,3-cyclohexadiene - 10:1
Nor
mal
ized
Inte
nsiti
es (a
.u.)
Time (min)
benzene:1,3-cyclohexadiene - 1:10
Figure S12: GC traces (method 2) of 3 combinations of benzene and 1,3-cyclohexadiene to emphasize the observable difference between the two different compounds for confirmation and comparison of the presence of benzene.
1 2 3 4 5 6 7 8 9 10 11 12
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
e
d
a
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention time (min)
b
c
Figure S13: GC traces of a mixture of full conversion metathesis (a), the mixture after dehydrogenation to benzene (b), subsequently hydrogenated (at 10 bar H2) mixture (c), enriched with dimethyl decanedioate (d), and additionally enriched with benzene (e).
S13
7.40 7.45 7.50 7.55 7.60 7.65 7.70 7.75 7.80
0.0
0.3
0.6
0.9
1.2
1.5
1.8
a
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
b
c
Figure S14: GC traces of a mixture of full conversion metathesis (a), the mixture after dehydrogenation to benzene (b), the subsequently hydrogenated (at 10 bar H2) mixture (c). Detail of the C8 region.
10.8 10.9 11.0 11.1 11.2 11.3
0.0
0.3
0.6
0.9
1.2
1.5
1.8
2.1
c
b
d
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S15: GC traces of a mixture of full conversion metathesis (a), the mixture after dehydrogenation to benzene (b), the subsequently hydrogenated (at 10 bar H2) mixture (c), enriched with dimethyl decanedioate (d). Detail of the C10 region.
S14
1 2 3 4 5 6 7 8 9 10 11 12
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
d
c
b
e
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S16: GC traces of a mixture of full conversion metathesis (a), the mixture after dehydrogenation to benzene (b), subsequently hydrogenated (at 5 bar H2) mixture (c), enriched with methyl octanoate (d), and additionally enriched with benzene (e).
7.40 7.45 7.50 7.55 7.60 7.65 7.70 7.75 7.80
0.0
0.5
1.0
1.5
2.0
d
c
b
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S17: GC traces of a mixture of full conversion metathesis (a), the mixture after dehydrogenation to benzene (b), subsequently hydrogenated (at 5 bar H2) mixture (c), enriched with methyl octanoate (d). Detail of the C8 region.
S15
10.8 10.9 11.0 11.1 11.2 11.3
0.00
0.25
0.50
0.75
1.00
1.25
c
b
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S18: GC traces of a mixture of full conversion metathesis (a), the mixture after dehydrogenation to benzene (b), subsequently hydrogenated (at 5 bar H2) mixture (c). Detail of the C10 region.
1 2 3 4 5 6 7 8 9 10 11 12
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
Nor
mal
ized
Inte
nsity
(a.u
)
Retention time (min) 188DP17_source 193DP17_PD source enrich sebMe octMe Benz_829 193DP17_PD source enrich sebMe octMe_781 193DP17_PD source enrich sebacicMe_755 193DP17_PD source_730
e
d
c
b
a
Figure S19: GC traces of the starting metathesis mixture (a), the mixture of (a) enriched with benzene and methyl octanoate and dimethyl decanedioate (b), enriched with methyl octanoate and dimethyl decanedioate (c) enriched with only dimethyl decanedioate (d), simultaneous dehydrogenation and hydrogenation (at 10 bar H2) of a metathesis mixture (e).
S16
1 2 3 4 5 6 7 8 9 10 11 12
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
e
d
c
b
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S20: GC traces of simultaneous dehydrogenation to aromatics and hydrogenation of alkenes at 5 bar H2 of a metathesis mixture (a), the mixture of (a) enriched with benzene and methyl octanoate (b), the starting metathesis mixture (c) simultaneous dehydrogenation and hydrogenation (at 5 bar H2) of a metathesis mixture (d), the mixture of (d) enriched with dimethyl decanedioate (e).
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0
0.0
0.3
0.6
0.9
1.2
1.5
1.8
c
b
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S21: GC traces of simultaneous dehydrogenation to aromatics and hydrogenation of alkenes at 5 bar H2 of a metathesis mixture (a), the mixture of (a) enriched with benzene and methyl octanoate (b), the starting metathesis mixture (c). Detail of the cyclic C6 region.
S17
7.40 7.45 7.50 7.55 7.60 7.65 7.70 7.75 7.80
0.0
0.5
1.0
1.5
c
b
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
a
Figure S22: GC traces of simultaneous dehydrogenation to aromatics and hydrogenation of alkenes at 5 bar H2 of a metathesis mixture (a), the mixture of (a) enriched with benzene and methyl octanoate (b), the starting metathesis mixture (c). Detail of the C8 region
10.8 10.9 11.0 11.1 11.2 11.3
0.0
0.3
0.6
0.9
1.2
1.5
1.8
e
d
c
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)Figure S23: GC traces of the starting metathesis mixture (c) simultaneous dehydrogenation to aromatics and hydrogenation of alkenes at 5 bar H2 of a metathesis mixture (d), the mixture of (d) enriched with dimethyl decanedioate (e). Detail of the C10 region.
S18
1 2 3 4 5 6 7 8 9 10 11 12
0,00,51,01,52,02,53,03,54,04,55,05,56,06,5
b
c
d
a
eNor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
f
Figure S24: GC traces of the mixture of (c) enriched with benzene and methyl octanoate (a), the mixture of (c) enriched with methyl octanoate (b), simultaneous dehydrogenation and hydrogenation at 1 bar H2 of a metathesis mixture (c), the starting metathesis mixture (d), the mixture of (f) enriched with dimethyl decanedioate (e) simultaneous dehydrogenation and hydrogenation at 1 bar H2 of a metathesis mixture enriched with methyl octanoate and benzene(f).
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
b
c
d
a
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)Figure S25: GC traces of mixtures the mixture of (c) enriched with benzene and methyl octanoate (a), the mixture of (c) enriched with methyl octanoate (b), simultaneous dehydrogenation and hydrogenation at 1 bar H2 of a metathesis mixture (c), the starting metathesis mixture (d). Detail of the cyclic C6 region.
S19
7.40 7.45 7.50 7.55 7.60 7.65 7.70 7.75 7.80-0.10.00.10.20.30.40.50.60.70.80.91.01.11.21.31.41.51.61.71.8
b
c
d
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
Figure S26: GC traces of the mixture of (c) enriched with methyl octanoate (b), simultaneous dehydrogenation to aromatics and hydrogenation of alkenes at 1 bar H2 of a metathesis mixture (c), the starting metathesis mixture (d). Detail of the cyclic C6 region.
10.8 10.9 11.0 11.1 11.2 11.3
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
c
d
e
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)Figure S27: GC traces of the simultaneous dehydrogenation to aromatics and hydrogenation of alkenes at 1 bar H2 of a metathesis mixture (c), the starting metathesis mixture (d), the mixture of (f) enriched with dimethyl decanedioate (e).
S20
3.90 3.95 4.00 4.05 4.10 4.15 4.20 4.25 4.30 4.35
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
0 min
15 min
30 min
60 min
120 min
240 min
360 min
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
Octane
octene isomers
4-octene
480 min
Figure S28: GC-traces of the samples taken at different time intervals during the hydrogenation of the model metathesis mixture, detail of the octene region (conditions see Graph S3).
13.0 13.1 13.2 13.3 13.4 13.5 13.6 13.7 13.8 13.9 14.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
oleic acid
isomers
stearic acid
0 min
15 min
30 min
60 min
120 min
240 min
360 min
480 min
Figure S29: GC-traces of the samples taken at different time intervals during the hydrogenation of the model metathesis mixture, detail of the oleic acid region (conditions see Graph S3).
S21
14.60 14.65 14.70 14.75 14.80 14.85 14.90 14.95 15.00
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
1,18-octadecenedioic acid
Nor
mal
ized
Inte
nsity
(a.u
.)
Retention Time (min)
1,18-octadecanedioic acid
0 min
15 min
30 min
60 min
120 min
240 min
360 min
480 min
Figure S30: GC-traces of the samples taken at different time intervals during the hydrogenation of the model metathesis mixture, detail of the oleic acid region (conditions see Graph S3).
NMR spectra
Figure S31: representative 1H NMR spectrum (400 MHz, CDCl3, 302K) of metathesis of EPA with Hoveyda-Grubs 2nd generation metathesis catalyst. The final ratio of 2:1 in 1,4-cyclohexadiene to octenoic acid is clearly seen from the integral values.
S22
Figure S32: representative 1H NMR spectrum (400 MHz, CDCl3, 302K) of dehydrogenation of 1,4-cyclohexadiene with Pd/C. Toluene is still present as it was used as solvent and not removed for measuring a 1H NMR spectrum.
References1 R. J. Rico, M. Page, C. Doubleday, J. Am. Chem. Soc. 1992, 114, 1131-1136.2 B. J. Dreyer, B. M. Pease, Methods for suppressing dehydrogenation, 2013, WO2013188200 (A1) 3 J. M. Krier, K. Komvopoulos, G. A. Somorjai, J. Phys. Chem. C 2016, 120, 8246-8250.4 R. A. Sheldon, J. M. Sobczak, J. Mol. Catal. 1991, 68, 1-6.5 A. V. Iosub, S. S. Stahl, J. Am. Chem. Soc. 2015, 137, 3454-3457.6 J. F. Quinn, D. A. Razzano, K. C. Golden, B. T. Gregg, Tetrahedron Lett. 2008, 49, 6137-6140.7 G. Fochi, Organometallics 1988, 7, 2255-2256.
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