Electronic Supplementary Information [ESI] Solar driven uphill conversion of dicyclopentadiene to cyclopentadiene: an

Transcription

1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information [ESI] Solar driven uphill conversion of dicyclopentadiene to cyclopentadiene: an important synthon for energy systems and fine chemicals Milan Dinda, a Supratim Chakraborty, a Mrinal Si, a Supravat Samanta, a Biswajit Ganguly, a,b Subarna Maiti,*,b and Pushpito K. Ghosh* a,b a Academy of Scientific & Innovative Research, CSIR-CSMCRI premises, G. B. Marg, Bhavnagar , India. b CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar , Gujarat, India pushpitokghosh@gmail.com (P. K. Ghosh); smaiti@csmcri.org (S. Maiti); Fax: Table of Contents Section Content Page S1 S2 Description of concentrators Figures S1 and S2 Weather, Insolation and Temperature related data Table S1; Figures S3 and S S3 1 H, 13 C NMR and HRMS data of S4 1 H, 13 C NMR data of S5 xyz co-ordinates of the following compounds optimized in CBS- QB3 level of theory. Free energy (G) and enthalpies (H) are given in Hartree unit

2 Description of parabolic dish concentrator employed for synthesis of cyclopentadiene (Cp) from dicyclopentadiene (5) The reaction was carried out in a solar parabolic dish concentrator constructed to bring about temperature of about 200 o C to 250 o C at the focus. The concentration ratio at the focus was calculated to be 20 X. Accordingly the parabola had the opening diameter (d0) of 1.38 m and focal length (f) of 0.34 m. The height (h) of the parabolic dish concentrator was 0.35 m. It was a semicircular trough made of poly-vinyl chloride plastic with small mirrors fixed on it to collect solar rays onto the focus where the glass round bottom flask was placed. The collector aperture area was 1.83 m 2 and the cross section of the opening of the parabola was 1.49 m 2. The dish had to be tracked according to the day long solar movement to get the maximum solar radiation on the flask at all times. Z d 0 d a Y X 2

3 Fig. S1 Experimental set-up for solar synthesis of Cp from 5 for (A) entries 1 and 2, Table 2, and (B) entry 3, Table 2. The only difference between (A) and (B) was that in the latter case the glass RB flask was painted black and inserted in a wooden box with transparent glass at the bottom and other interiors of the box painted black. 3

4 Description of offset parabola employed for the synthesis of 7 An offset parabolic type of solar dish collector with width of 0.62 m, diameter of 0.68 m and depth of 0.05 m was fabricated. 24 pieces of anodized aluminum reflector were joined in such a way that the focus was at 0.43 m. The concentration ratio was calculated to be 59 X to achieve a maximum temperature of 200 o C at the focus considering the ambient conditions prevailing. Fig. S2 Picture of experimental set-up for synthesis of 7 4

5 Temperature ( o C) solar Intensity ( W/m 2 ) Temperature ( o C) solar Intensity ( W/m 2 ) A Time of the day (h) B Time of the day (h) Fig. S3 Global insolation (green), ambient temperature (blue) and reaction temperature (red) recorded during the reactions of (A) Entry 2, Table 2 and (B) Entry 3, Table 2. 5

6 Table S1 Other weather related measurements during the reaction of Entry 2, Table 2. Time/ HH:MM Wind Speed/ m sec -1 Wind Dir./ Atm. Pressure/ mbar 10: : : : : : : : :

7 Temperature o C Time of day Reaction temperature T Ambient T Fig. S4 Temperature profile during the reaction of eqn. 5 7

8 Solar mediated synthesis of 1-(3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-yl) ethanone (7) 1 H NMR 8

9 13 C NMR 9

10 HRMS of 1-(3-phenylbicyclo[2.2.1]hepta-2,5-dien-2-yl) ethanone (7) 10

11 Solar mediated synthesis of Pentacyclo-[ ,6.0 3, ,9 )undecan-8, 11 dione (9) 1 H NMR 11

12 13 C NMR 12

13 xyz co-ordinates of compounds optimized at CBS-QB3 level of theory. Free energy (G) and enthalpies (H) are given in Hartree unit. Compound-1 H= G= C C C C H H C H H C H C H H H Compound-2 H= G= C C C C H H C Compound-7 H= G= C C C C C H H C C H H H H C O C H H H C C C C H C

14 H H C H C H C H H H H H H Compound-5 H= G= C C C H H C H C H H H C H H C H C H C Compound-8 H= G= C C C C C H H C C H H H H C C C C O O H H

15 H C H H H Compound-9 H= Acetylene H= G= C H C H Cyclopentadiene H= G= C C C C C H H H H H H G= C C C C H H C H H C C H H C C C C O O H H H H