Electronic Supplementary Material (ESI) for Science & Technology. This journal is © The Royal Society of Chemistry 2014

Supplementary material: Deoxydehydration of to catalyzed by rhenium compounds

By

Valentino Canale,a Lucia Tonucci,b Mario Bressan,a and Nicola d’Alessandro*a

a Department of Engineering and Geology (INGEO), “G. d’Annunzio” University of Chieti-

Pescara, Viale Pindaro, 42, 65127 Pescara, Italy

b Department of Philosophical, Educational and Economic Science, “G. d’Annunzio” University of

Chieti-Pescara, Via dei Vestini, 31, 66013 Chieti Scalo, Italy

c

1 8

6 alcohol

allyl

of 4 %

Molar 2

0 0 50 100 150 200 250 300 350 400 Reaction time (min)

Figure S1: Time course of the DODH reaction (beginning) at 140 °C in neat glycerol and in presence of MTO, under air bubbling.

2 2.4

1.9 alcohol

allyl 1.4

of

%

0.9 Molar 0.4

-0.1 0 10 20 30 40 50 60 70

Reaction time (min)

Figure S2: Time course of the DODH reaction (beginning) at 140 °C in neat glycerol and in presence of ReO3, under air bubbling.

3 20 18 16

alcohol 14

12 allyl

of 10 %

8

Molar 6 4 2 0 0 100 200 300 400 500 600 700 800 Reaction time (min)

Figure S3: Time-course of the DODH reaction in neat glycerol, in presence of MTO, in air (continuous lines) or nitrogen (dotted lines) and at 140 °C (circles) or 170 °C (triangles)

4 35

30 alcohol

25 allyl 20 of

% 15

Molar 10

5

0 0 200 400 600 800 1000 1200 1400 1600 Reaction time (min)

Figure S4: Time-course of the DODH reaction in neat glycerol, in presence of ReO3, in air (continuous lines) or nitrogen (dotted lines) and at 140 °C (circles) or 170 °C (triangles)

5 RT: 0.00 - 10.86 SM: 7G 2.10 NL: 100 3.26E8 TIC MS 95 allilico+ acroleina0, 90 1M

85

80

75

70

65

60 e c n

a 55 d n u b 50 A

e v i t

a 45 l e R 40

35

30

25

20 2.31

15

10 1.84 9.62 10.19 5 9.05 7.00 7.26 7.80 8.50 0.33 0.55 1.05 2.52 3.07 4.21 4.35 5.23 5.48 6.51 0 0 1 2 3 4 5 6 7 8 9 10 Time (min)

Figure S5: Headspace-GC-MS chromatogram of an aqueous solution of 0.1 M of acrolein (time 2.10 min) and 0.1 M of allyl alcohol (time 2.31 min). The ratio of the two areas is 5.81. For the conditions see the experimental section.

6 RT: 0.00 - 10.85 SM: 7G 1.82 NL: 100 2.20E7 front of the chromatogram TIC MS 95 2.28 allilicoH2m 455 90

85 allyl alcohol

80

75

70

65

60 e acrolein c n

a 55 d n u b 50 A

e v i t

a 45 l diallyl ether e

R 3.31 40

35

30

25 allyl formate 20 2.60 allyl 15 10.30 10.54 8.79 9.91 10 3.38 7.79 8.55 7.13 7.21 9.26 5 0.36 0.76 1.55 3.05 3.52 4.34 5.30 5.61 6.51

0 0 1 2 3 4 5 6 7 8 9 10 Time (min)

Figure S6: Headspace-GC-MS chromatogram of the aqueous trap. The DODH reaction was performed in neat glycerol, with MTO, under H2 bubbling, at 140 °C (455 min. of reaction time).

7 Figure S7: 1H NMR of the aqueous trap. The DODH reaction was performed in 2,4-dimhetyl-3-pentanol, with ReO3, under H2 bubbling, at 140 °C (390 min. of reaction time). Together with allyl alcohol (4, 5.2 and 5.9 ppm) inside the spectra appear the signals of the solvent and of its oxidation derivative (ketone).

8 RT: 0.00 - 10.86 SM: 7G NL: 12.5 3.07E8 12.0 TIC MS allilicH21es 11.5 anolo140C 960m50mL 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 e c

n 7.0 a d n

u 6.5 b 1.83 A

e 6.0 2.30 5.86 v i t a l 5.5 e R 5.0 4.5 4.0

3.5 4.37 3.0

2.5 2.0 4.13 1.5 3.93 6.40 7.10 8.08 1.0 10.26 3.32 5.02 8.78 9.44 10.04 3.07 3.41 7.80 0.5 0.64 1.21 0.0 0 1 2 3 4 5 6 7 8 9 10 Time (min)

Figure S8: Headspace-GC-MS chromatogram of the aqueous trap. The DODH reaction was performed in 1- hexanol, with MTO, under H2 bubbling, at 140 °C (960 min. of reaction time). Among the peaks present in the middle part of the chromatogram, all attributable to the solvent of the DODH reaction, note hexanal (4.57 min) and 1-hexanol (5.17 min).

9 Reaction mixture

Methane

Standard

Figure S9: Methane detection by headspace-GC FID analysis of the DODH reaction conducted in neat glycerol, in presence of MTO and under air bubbling at 140 °C.

10 100.00

80.00 MTO 60.00 %

40.00

20.00

0.00 0 20 40 60 80 100 120 140 160 180 200 Reaction time (min)

Figure S10: Residual content of MTO, as measured by the 1H NMR signal (area) of the methyl groups: reaction performed in 2,4-dimethyl-3-pentanol under air bubbling at 140°C.

11 90.00 80.00 70.00 60.00 % allyl alchool 50.00 40.00 30.00 20.00 10.00 0.00 0 200 400 600 800 1000 1200 1400 reaction time (min)

Figure S11: MTO catalysed DODH reactions in 2,4-dimethyl-3-pentanol under deuterium (stars) or hydrogen (circles) bubbling at 140°C.

12