γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full...

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ELECTRONIC SUPPORTING INFORMATION γ-Valerolactone as an alternative biomass-derived medium for the Sonogashira reaction Giacomo Strappaveccia, [a] Lorenzo Luciani, [a] Elena Bartollini, [a] Assunta Marrocchi, [a] Ferdinando Pizzo, [a] Luigi Vaccaro *[a] [a] Laboratory of Green Synthetic Organic Chemistry, CEMIN – Dipartimento di Chimica, Università di Perugia Via Elce di Sotto 8, 06123 Perugia, Italia, E-mail: [email protected] CONTENTS page ESI 1 Experimental Section page ESI 2-ESI 21 Full characterization data ( 1 H NMR, 13 C NMR, 19 F NMR, EA, GC-EIMS) for Compounds 3 a-q page ESI 23-ESI 53 Copies of the 1 H, 13 C NMR and 19 F NMR for compounds 3 a-q ESI - 1 Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2014

Transcript of γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full...

Page 1: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

ELECTRONIC SUPPORTING INFORMATION

γ-Valerolactone as an alternative biomass-derived medium for theSonogashira reaction

Giacomo Strappaveccia,[a] Lorenzo Luciani,[a] Elena Bartollini,[a] Assunta Marrocchi,[a] Ferdinando

Pizzo,[a] Luigi Vaccaro*[a]

[a] Laboratory of Green Synthetic Organic Chemistry, CEMIN – Dipartimento di Chimica, Università

di Perugia Via Elce di Sotto 8, 06123 Perugia, Italia, E-mail: [email protected]

CONTENTS

page ESI 1 Experimental Section

page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for

Compounds 3 a-q

page ESI 23-ESI 53 Copies of the 1H, 13C NMR and 19F NMR for compounds 3 a-q

ESI - 1

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

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Experimental Section

Unless otherwise stated, all solvents and reagents were used as obtained from Sigma-Aldrich Co.

without further purification. Commercial Pd/C (10% wt) was not activated prior to use, and the

value of palladium loading was taken from its certificate of analysis available at

http://www.sigmaaldrich.com. GLC analyses were performed by using Hewlett-Packard HP 5890A

equipped with a capillary column DB-35MS (30 m, 0.53 mm), a FID detector and hydrogen as gas

carrier. GC-EIMS analyses were carried out by using a Hewlett-Packard HP 6890N Network GC

system/5975 Mass Selective Detector equipped with an electron impact ionizer at 70 eV. NMR

spectra were recorded on a Bruker DRX-ADVANCE 400 MHz (1H at 400 MHz, 13C at 100.6 MHz

and 19F at 376.4 MHz) in CDCl3 using TMS as the internal standard. Elemental Analyses were

conducted on a Fisons EA1108CHN. Melting points are not corrected and they were measured on

a Büchi 510. An Inductive Coupled Plasma-Optical Emission Spectrometer (ICP-OES 710 Agilent

Technology) was used to determine the amount of leached palladium into the reaction products.

Compounds 3a,1 3b,1 3c,1 3d,2 3e,1 3f,1 3g,3 3h,4 3i,4 3j,4 3k,5 3l,4 3m,5 3n,6 3o,6 3p,6 3q7 are

known compounds.

Characterization data and copies of the 1H and 13C NMR are reported below.

Reference:

(1) A. Modak, J. Mondal, A. Bhaumik, Green Chem. 2012, 14, 2840–2855 (2) K. Worm-Leonhard, M. Meldal, Eur. J. Org. Chem., 2008, 31, 5244-5253 (3) R. Thorwirth, A. Stolle, B. Ondruschka, Green Chem., 2010, 12, 985-991 (4) S. Mori, T. Yanase, S. Aoyagi, Y. Monguchi, T. Maegawa, H. Sajiki, Chem. Eur. J., 2008, 14,

6994-6999 (5) Y. Shi, X. Li, J. Liu, W. Jiang, L. Sun, Appl. Organometal. Chem., 2011, 25, 514-520 (6) S. Urgaonkar, J. G. Verkade, J. Org. Chem., 2004, 69, 5752-5755 (7) L. Yang, Y. Li, Q. Chen, Y. Du, C. Cao, Y. Shi, G. Pang, Tetrahedron, 2013, 69, 5178-5184 (8) K. Takahashi, Y. Kuroyama, K. Sonogashira, N. Hagihara, Synthesis, 1980, 627-630

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Chem. Name 1,2-diphenylethyne (3a)

Lit. Ref. Green Chem., 2012, 14, 2840–2855

METHOD: In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), iodobenzene (1a) (139 mg, 0.114 mL, 1 mmol, 98% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (petroleum ether) to afford 3a as a white solid (124 mg, 70% yield). Mol Formula C14H10 m.p. 61-63 °C

Elemental Analysis: Calc.: C: 94.34; H: 5.66; found C: 94.24; H: 5.60

1H NMR 400 MHz CDCl3

δ value No. H Mult. j value/Hz

7.34-7.36 6 m

7.53-7.55 4 m

13C NMR (100.6 MHz, CDCl3) δ : 89.37; 123.28; 128.25; 128.34; 131.61

GC-EIMS (m/z, %): 178 (M+, 100), 177 (34), 176 (50), 152 (29), 151 (21), 150 (15), 126 (12), 89 (15)

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Chem. Name 1-nitro-4-(phenylethynyl)benzene (3b)

Lit. Ref. Green Chem., 2012, 14, 2840–2855

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-iodo-4-nitrobenzene (1b) (254 mg, 1 mmol, 98% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 2 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / toluene / petroleum ether) to afford 3b as a white solid (210 mg, 94% yield).

Mol Formula C14H9NO2 m.p. 116-118 °C

Elemental Analysis: Calc.: C: 75.33; H: 4.06; N:6.27; found C: 75.10; H: 4.99; N: 6.20

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.39-7.41 3 m

7.55-7.58 2 m

7.67 2 d 8.7

8.23 2 d 8.7

13C NMR (100.6 MHz, CDCl3) δ : 87.6, 94.7, 122.1, 123.6, 128.6, 129.3,130.3, 131.9, 132.3, 147.0

GC-EIMS (m/z, %): 223 (M+, 100), 193 (29), 176 (60), 165 (27), 177 (19), 151 (20), 150 (16)

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Chem. Name 1-(4-(phenylethynyl)phenyl)ethanone (3c)

Lit. Ref. Green Chem., 2012, 14, 2840–2855

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-(4-iodophenyl)ethanone (1c) (251 mg, 1 mmol, 98% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 2.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / toluene : petroleum ether) to afford 3c as a white solid (209 mg, 95% yield).

Mol Formula C16H12O m.p. 98-101 °C

Elemental Analysis: Calc.: C, 87.25; H, 5.49; found C: 87.00; H: 5.40

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

2.63 3 s

7.37-7.38 3 m

7.55-7.57 2 m

7.61 2 d 8.3

7.94 2 d 8.3

13C NMR (100.6 MHz, CDCl3) δ : 26.6, 88.6, 92.7, 122.6, 128.2, 128.3, 128.4, 128.8, 131.69, 131.73, 136.2, 197.3

GC-EIMS (m/z, %): 220 (M+, 61), 205 (100), 177 (24), 176 (55), 151 (21), 150 (17), 88 (10), 43 (10)

Chem. Name 4-(phenylethynyl)benzaldehyde (3d)

Lit. Ref. Eur. J. Org. Chem., 2008, 31, 5244-5253

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METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 4-iodobenzaldehyde (1d) (234 mg, 1 mmol, 96% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 2.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / toluene : petroleum ether) to afford 3d as a white solid (186 mg, 90% yield).

Mol Formula C15H10O m.p. 95-97 °C

Elemental Analysis: Calc.: C, 87.36; H, 4.89; found C: 87.10; H:4.80

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.38 3 br

7.56 2 br

7.68 2 d 7.8

7.87 2 d 7.8

10.02 1 s 13C NMR (100.6 MHz, CDCl3) δ : 88.5, 93.5, 122.5, 128.5, 129.0, 129.6, 131.8, 132.1, 135.4, 191.5

GC-EIMS (m/z, %): 206 (M+, 100), 205 (71), 178 (14), 177 (20), 176 (51), 151 (20), 150 (17)

Chem. Name 1-methyl-4-(phenylethynyl)benzene (3e)

Lit. Ref. Green Chem., 2012, 14, 2840–2855

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METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-iodo-4-methylbenzene (1e) (220 mg, 1 mmol, 99% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (petroleum ether) to afford 3e as a white solid (154 mg, 80% yield).

Mol Formula C15H12 m.p. 67-70 °C

Elemental Analysis: Calc.: C: 93.71; H: 6.29; found C: 93.63; H: 6.19

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

2.37 3 s

7.16 2 d 7.8

7.33-7.36 3 m

7.43 2 d 7.9

7.52-7.54 2 m 13C NMR (100.6 MHz, CDCl3) δ : 21.5, 88.7, 89.6, 120.2, 123.5, 128.1, 128.3, 129.1, 131.5, 131.6, 138.4

GC-EIMS (m/z, %): 192 (M+, 100), 191 (100), 190 (32), 189 (47), 165 (27), 115 (10), 94 (11), 82 (10)

Chem. Name 1-methoxy-4-(phenylethynyl)benzene (3f)

Lit. Ref. Green Chem., 2012, 14, 2840–2855

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METHOD: In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt.(5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-iodo-4-methoxybenzene (1f) (238 mg, 1 mmol, 98% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / toluene : petroleum ether) to afford 3f as a white solid (156 mg, 75% yield).

Mol Formula C15H12O m.p. 58-61 °C

Elemental Analysis: Calc.: C: 86.51; H: 5.81; found C: 86.40; H: 5.75

1H NMR 400 MHz

CDCl3

δ value No. H Mult. j value/Hz

3.83 3 s

6.88 2 d 8.6

7.26-7.35 3 m

7.46-7.52 4 m

13C NMR (100.6 MHz, CDCl3) δ : 55.3, 88.0, 89.3, 114.0, 115.4, 123.6, 127.9, 128.3, 131.4, 133.0, 159.6

GC-EIMS (m/z, %): 208 (M+, 100), 193 (10), 165 (48), 164 (17), 163 (13), 139 (13)

Chem. Name 2-(phenylethynyl)thiophene (3g)

Lit. Ref. Green Chem., 2010, 12, 985-991

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METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 2-iodothiophene (1g) (215 mg, 0.113 mL, 1 mmol, 98% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 6 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 MHCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (petroleum ether) to afford 3g as a white solid (120 mg, 65% yield).

Mol Formula C12H8S m.p. 50-52 °C

Elemental Analysis: Calc.: C: 78.22; H: 4.38; S: 17.40 found C: 78.19; H: 4.30, S:17.38

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.00-7.02 1 m

7.29-7.30 2 m

7.34-7.35 3 m

7.51-7.53 2 m 13C NMR (100.6 MHz, CDCl3) δ : 82.6, 93.0, 122.9, 123.3, 127.1, 127.2, 128.4, 128.4, 129.2, 131.4, 131.9, 132.5

GC-EIMS (m/z, %): 184 (M+, 100), 183 (8), 152 (16), 139 (25), 126 (10), 113 (5), 98 (5)

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Chem. Name 1-nitro-4-(phenylethynyl)benzene (3b)

Lit. Ref. Green Chem., 2012, 14, 2840–2855

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-Bromo-4-nitrobenzene (1h) (204 mg, 1 mmol, 99% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 12 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / toluene / petroleum ether) to afford 3b as a white solid (167 mg, 75% yield).

Mol Formula C14H9NO2 m.p. 116-118 °C

Elemental Analysis: Calc.: C: 75.33; H: 4.06; N:6.27; found C: 75.10; H: 4.99; N: 6.20

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.39-7.41 3 m

7.55-7.58 2 m

7.67 2 d 8.7

8.23 2 d 8.7

13C NMR (100.6 MHz, CDCl3) δ : 87.6, 94.7, 122.1, 123.6, 128.6, 129.3,130.24, 131.9, 132.3, 147.0

GC-EIMS (m/z, %): 223 (M+, 100), 193 (29), 176 (60), 165 (27), 177 (19), 151 (20), 150 (16)

Chem. Name 4-(phenylethynyl)benzaldehyde (3d)

Lit. Ref. Eur. J. Org. Chem., 2008, 31, 5244-5253

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METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol 4-Bromobenzaldehyde (1i) (187 mg, 1 mmol, 99% purity), and ethynylbenzene (2a) (156 mg, 0.168 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 12 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / toluene : petroleum ether) to afford 3d as a white solid (145 mg, 70% yield).

Mol Formula C15H10O m.p. 95-97 °C

Elemental Analysis: Calc.: C, 87.36; H, 4.89; found C: 87.10; H:4.80

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.38 3 br

7.55 2 br

7.68 2 d 7.8

7.87 2 d 7.8

10.02 1 s 13C NMR (100.6 MHz, CDCl3) δ : 88.5, 93.5, 122.5, 128.5, 129.0, 129.6, 131.8, 132.1, 135.4, 191.5

GC-EIMS (m/z, %): 206 (M+, 100), 205 (71), 178 (14), 177 (20), 176 (51), 151 (20), 150 (17)

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Chem. Name 1-(phenylethynyl)-2-(trifluoromethyl)benzene (3h)

Lit. Ref. Chem. Eur. J., 2008, 14, 6994-6999

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), iodobenzene (1a) (139 mg, 0.114 mL, 1 mmol, 98% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to obtain 3h as a white solid (182 mg, 74% yield).

Mol Formula C15H9F3 m.p. 70-73 °C

Elemental Analysis: Calc.: C: 73.17; H: 3.68; found C: 73.00; H: 3.60

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.36-7.43 4 m

7.50-7.56 3 m

7.66-7.69 2 m

13C NMR (100.6 MHz, CDCl3) δ: 85.3; 94.9; 121.6, 122.2, 122.7; 125.0, 125.9 (q, jF-

C= 5.0 Hz), 127.9, 128.4, 128.8, 131.4, 131.7, 133.7

19F NMR(376.4,CDCl3) δ : -62.7

GC-EIMS (m/z, %): 246 (M+, 100), 245 (51), 227 (18), 225 (23), 207 (6), 196 (10)

Chem. Name 1-((4-nitrophenyl)ethynyl)-2-(trifluoromethyl)benzene (3i)

Lit. Ref. Chem. Eur. J., 2008, 14, 6994-6999

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METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-iodo-4-nitrobenzene (1b) (254 mg, 1 mmol, 98% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 2 hours, petroleum ether was added and the reaction mixturewas filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether: toluene) to afford 3i as a pale yellow solid (265 mg, 91% yield).

Mol Formula C15H8F3NO2 m.p. 95-98 °C

Elemental Analysis: Calc.: C: 61.86; H: 2.77; N: 4.81; found C: 61.76; H: 2.70; N: 4.79

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.47-7.51 1 m

7.54-7.58 1 m

7.66-7.73 4 m

8.23 2 d 8.5

13C NMR (100.6 MHz, CDCl3) δ : 90.6, 93.0, 120.7, 122.5, 124.1, 125.2, 126.6 (q, jF-

C= 4.9 Hz), 129.4, 129.9, 132.0, 132.4, 132.8, 134.4, 147.7

19F NMR(376.4,CDCl3) δ : -62.6

GC-EIMS (m/z, %): 291 (M+, 100), 261 (19), 245 (24), 243 (10), 233 (24), 232 (24), 225 (34), 214 (12)

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Chem. Name 1-(4-((2-(trifluoromethyl)phenyl)ethynyl)phenyl)ethanone (3j)

Lit. Ref. Chem. Eur. J., 2008, 14, 6994-6999

+

1c

Pd/C (0.5 mol%)DABCO (1.2 eq.)

2b

1.5 eq.

I

1 eq.

M.W.: 288

3j

O

OGVL (1 M), 60°C, 2.5 h, N2

F3C F3C

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-(4-iodophenyl)ethanone (1c) (251 mg, 1 mmol, 98% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 2.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to obtain 3jas a white solid (277 mg, 96% yield).

Mol Formula C17H11F3O m.p. 80-83 °C

Elemental Analysis: Calc.: C: 70.83; H: 3.85; found C:70.79; H: 3.80

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

2.62 3 s

7.46-7.48 1 m

7.53-7.57 1 m

7.63 2 d 8.1

7.68-7.72 2 m

7.96 2 d 8.1 13C NMR (100.6 MHz, CDCl3) δ : 26.7, 88.4, 93.8, 120.9, 122.2, 124.9, 126.0 (q, jF-

C= 4.9 Hz), 127.5, 128.3, 128.5, 131.5, 131.8, 133.8, 136.6, 197.3

19F NMR(376.4, CDCl3) δ : -62.7

GC-EIMS (m/z, %): 288 (M+, 49), 274 (17), 273 (100), 245 (29), 243 (8), 225 (29), 219 (6), 214 (6)

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Chem. Name 1-(p-tolylethynyl)-2-(trifluoromethyl)benzene (3k)

Lit. Ref. Appl. Organometal. Chem., 2011, 25, 514-520

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-iodo-4-methylbenzene (1e) (220 mg, 1 mmol, 99% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (petroleum ether) to afford 3k as a white solid (182 mg, 70% yield).

Mol Formula C16H11F3 m.p. 73-75 °C

Elemental Analysis: Calc.: C: 73.84; H: 4.26; found C: 73.79; H: 4.25

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

2.38 3 s

7.18 2 d 7.6

7.38-7.53 4 m

7.65-7.69 2 m

13C NMR (100.6 MHz, CDCl3) δ : 21.5, 84.8, 95.2, 119.7, 121.8, 122.3, 125.0, 125.9 (q, jF-C= 4.8 Hz), 127.7, 129.2, 131.4, 131.6, 133.6, 139.1

19F NMR(376.4,CDCl3) δ : -62.6

GC-EIMS (m/z, %): 260 (M+, 100), 259 (26), 239 (21), 238 (25), 221 (9), 220 (20),189 (11)

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Chem. Name 1-((4-methoxyphenyl)ethynyl)-2-(trifluoromethyl)benzene (3l)

Lit. Ref. Chem. Eur. J., 2008, 14, 6994-6999

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-iodo-4-methoxybenzene (1f) (238 mg, 1 mmol, 98% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to afford 3l as a white solid (180 mg, 65% yield).

Mol Formula C16H11F3O m.p. 64-67 °C

Elemental Analysis: Calc.: C: 69.56; H: 4.01; found C: 69.49; H: 3.99

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

3.84 3 s

6.89 2 d 8

7.36-7.40 1 m

7.49 3 d 8

7.63-7.68 2 m

13C NMR (100.6 MHz, CDCl3) δ : 55.3, 84.2, 95.1, 114.0, 114.8, 121.9, 122.3, 125.0, 125.9 (q, jF-C= 4.8 Hz), 127.5, 131.3, 133.2, 133.4, 160.1

19F NMR(376.4,CDCl3) δ : -62.9

GC-EIMS (m/z, %): 276 (M+, 100), 261 (19), 233 (27), 232 (43), 214 (9), 183 (14)

Chem. Name 2-((2-(trifluoromethyl)phenyl)ethynyl)thiophene (3m)

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Lit. Ref. Appl. Organometal. Chem., 2011, 25, 514-520

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 2-iodothiophene (1g) (215 mg, 0.113 mL, 1 mmol, 98% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 6 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (petroleum ether) to obtain 3m as a white solid (151 mg, 60% yield).

Mol Formula C13H7F3S m.p. 55-56 °C

Elemental Analysis: Calc.: C: 61.90; H: 2.80; S: 12.71; found C: 61.88, H: 2.78, S: 12.67

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.04-7.06 1 m

7.35-7.36 2 m

7.42-7.43 1 m

7.50-7.54 1 m

7.65-7.70 2 m

13C NMR (100.6 MHz, CDCl3) δ : 88.3, 89.1, 121.2, 122.2, 122.6, 124.9, 125.9 (q, jF-

C= 4.9 Hz), 127.2, 128.0, 128.2, 131.4, 132.7, 133.4

19F NMR(376.4,CDCl3) δ : -62.7

GC-EIMS (m/z, %): 252 (M+, 100), 233 (32), 219 (11), 207 (9), 206 (11), 202 (10), 188 (10)

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Chem. Name 1-((4-nitrophenyl)ethynyl)-2-(trifluoromethyl)benzene (3i)

Lit. Ref. Chem. Eur. J., 2008, 14, 6994-6999

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (139 mg, 1.2 mmol, 99% purity), 1-bromo-4-nitrobenzene (1h) (204 mg, 1 mmol, 99% purity), and 1-ethynyl-2-(trifluoromethyl)benzene (2b) (263 mg, 0.215 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 12 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to afford 3i as a white solid (224 mg, 77% yield).

Mol Formula C15H8F3NO2 m.p. 95-98 °C

Elemental Analysis: Calc.: C: 61.86; H: 2.77; N: 4.81; found C: 61.76; H: 2.70; N: 4.79

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

7.47-7.51 1 m

7.54-7.58 1 m

7.66-7.73 4 m

8.23 2 d 8.5

13C NMR (100.6 MHz, CDCl3) δ : 90.6, 93.0, 120.7, 122.5, 124.1, 125.2, 126.6 (q, jF-

C= 4.9 Hz), 129.4, 129.9, 132.0, 132.4, 132.8, 134.4, 147.7

19F NMR(376.4,CDCl3) δ : 62.6

GC-EIMS (m/z, %): 291 (M+, 100), 261 (19), 245 (24), 243 (10), 233 (24), 232 (24), 225 (34), 214 (12)

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Chem. Name 1-nitro-4-(oct-1-ynyl)benzene (3n)

Lit. Ref. J. Org. Chem., 2004, 69, 5752-5755

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (231 mg, 2 mmol, 99% purity), 1-iodo-4-nitrobenzene (1b) (254 mg, 1 mmol, 98% purity), and oct-1-yne (2c) (172 mg, 0.230 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to afford 3n as an oil (218 mg, 94% yield).

Mol Formula C14H17NO2 m.p. oil

Elemental Analysis: Calc.: C: 71.87; H: 6.96; N: 6.06; found C: 71.80; H: 6.90; N: 6.00

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

0.91 3 t 6.6

1.32-1.34 4 m

1.42-1.49 2 m

1.58 -1.66 2 m

2.44 2 t 7.1

7.51 2 d 8.7

8.15 2 d 8.7

13C NMR (100.6 MHz, CDCl3) δ : 14.0; 19.6; 22.5; 28.3; 28.6; 31.3; 79.3; 96.2; 123.5; 131.2; 132.2; 146.6

GC-EIMS (m/z, %): 231 (M+, 21), 202 (60), 188 (51), 156 (45), 142 (71), 141 (53), 128 (100), 129 (54), 114 (45), 115 (75), 116 (46)

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Chem. Name 1-(4-(oct-1-ynyl)phenyl)ethanone (3o)

Lit. Ref. J. Org. Chem., 2004, 69, 5752-5755

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (231 mg, 2 mmol, 99% purity), 1-(4-iodophenyl)ethanone (1c) (251 mg, 1 mmol, 98% purity), and oct-1-yne (2c) (172 mg, 0.230 mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to afford 3o as an oil (220 mg, 96% yield).

Mol Formula C16H20O m.p. oil

Elemental Analysis: Calc.: C: 84.16; H: 8.83; found C: 84.10; H: 8.79

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

0.91 3 t 6.4

1.24-1.33 4 m

1.42-1.49 2 m

1.59-1.65 2 m

2.43 2 t 7.1

2.61 3 s

7.46 2 d 8.2

7.87 2 d 8.2

13C NMR (100.6 MHz, CDCl3) δ : 14.0; 19.5; 22.5; 26.6; 28.5; 28.6; 31.3; 80.1; 94.4; 128.1; 129.2; 131.6; 135.6; 197.4

GC-EIMS (m/z, %): 228 (M+, 26), 213 (48), 157 (25), 143 (25), 129 (51), 128 (28), 115 (28), 114 (33)

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Chem. Name

1-(hex-1-ynyl)-4-nitrobenzene (3p)

Lit. Ref. Tetrahedron, 2013, 69, 5178-5184

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (231 mg, 2 mmol, 99% purity), 1-iodo-4-nitrobenzene (1b) (254 mg, 1 mmol, 98% purity), and hex-1-yne (2d) (127 mg, 0.178mL, 1.5 mmol, 97% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 4.5 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washedwith neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether: toluene) to afford 3p as an oil (177 mg, 87% yield).

Mol Formula C12H13NO2 m.p. oil

Elemental Analysis: Calc.: C: 70.92; H: 6.45; N: 6.89; found C: 70.89; H: 6.40; N: 6.80

1H NMR

400 MHz

CDCl3

δ value No. H Mult. j value/Hz

0.96 3 t 7.2

1.45-1.53 2 m

1.57-1.65 2 m

2.45 2 t 7.1

7.51 2 d 8.7

8.14 2 d 8.7

13C NMR (100.6 MHz, CDCl3) δ :13.6; 19.2; 22.0; 30.4; 79.3; 96.8; 123.5; 131.2; 132.2; 146.5

GC-EIMS (m/z, %): 203 (M+, 66),188 (100), 156 (33), 142 (94), 128 (93), 114 (46), 115 (71),102 (39),63 (29)

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Chem. Name trimethyl((4-nitrophenyl)ethynyl)silane (3q)

Lit. Ref. Synthesis, 1980, 627-630

METHOD:

In a screw capped vial equipped with a magnetic stirrer Pd/C 10% wt. (5.3 mg, 0.005 mmol), GVL (1 mL, 98% purity), DABCO (231 mg, 2 mmol, 99% purity), 1-iodo-4-nitrobenzene (1b) (254 mg, 1 mmol, 98% purity), and ethynyltrimethylsilane (2e) (150 mg, 0.216 mL, 1.5 mmol, 98% purity) were consecutively added, the resulting mixture was purged with nitrogen and left under stirring at 60 °C. After 6 hours, petroleum ether was added and the reaction mixture was filtered over a small pad of celite, washed with neutral water and, subsequently, with acidic water (1 M HCl). The organic layer was dried over sodium sulphate and the solvent was removed under vacuum. The crude oil was purified by column chromatography on silica gel (1:1 / petroleum ether : toluene) to afford 3q as a white solid (134 mg, 61% yield).

Mol Formula C11H13NO2Si m.p. 98-100 °C

Elemental Analysis: Calc.: C: 60.24; H: 5.97; N: 6.39; found C: 60.00; H: 5.90; N: 6.00

1H NMR

400 MHz CDCl3

CDCl3

δ value No. H Mult. j value/Hz

0.27 9 s

7.59 2 d 8.6

8.17 2 d 8.6

13C NMR (100.6 MHz, CDCl3) δ : -0.3, 100.6, 102.7, 123.5, 130.0, 132.7, 147.1

GC-EIMS (m/z, %): 219 (M+,16), 205 (22), 204 (100), 158 (35), 145 (9), 143 (17), 117 (7)

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7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.26

47.

343

7.34

67.

359

7.52

97.

533

7.54

5

2.99

12.

000

1,2−diphenylethyne (3a)

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140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

76.7

0077

.019

77.3

36

89.3

72

123.

281

128.

254

128.

344

131.

612

1,2−diphenylethyne (3a)

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8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.26

37.

394

7.40

37.

407

7.55

67.

566

7.57

47.

579

7.66

47.

686

8.22

08.

242

3.21

02.

151

2.08

1

2.00

0

1−nitro−4−(phenylethynyl)benzene (3b)

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150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

76.7

2477

.042

77.3

59

87.5

61

94.7

18

122.

087

123.

653

128.

555

129.

299

130.

267

131.

855

132.

271

146.

951

1−nitro−4−(phenylethynyl)benzene (3b)

ESI - 26

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8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.62

4

7.26

47.

369

7.37

77.

385

7.52

37.

547

7.55

37.

557

7.56

27.

570

7.60

77.

628

7.93

97.

960

2.87

9

3.30

62.

144

2.04

0

2.00

0

1−(4−(phenylethynyl)phenyl)ethanone (3c)

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2030405060708090100110120130140150160170180190 ppm

26.6

10

76.6

8477

.002

77.3

19

88.5

9292

.703

122.

644

128.

204

128.

266

128.

436

128.

805

131.

690

131.

734

136.

188

197.

323

1−(4−(phenylethynyl)phenyl)ethanone (3c)

128.0128.5129.0 ppm

128.

204

128.

266

128.

436

128.

805

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10 9 8 7 6 5 4 3 2 1 ppm

7.26

07.

385

7.55

97.

670

7.69

07.

862

7.88

2

10.0

24

3.18

12.

118

2.04

82.

041

1.00

0

4−(phenylethynyl)benzaldehyde (3d)

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190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

76.7

3977

.056

77.3

74

88.5

31

93.4

61

122.

468

128.

497

128.

994

129.

604

131.

798

132.

110

135.

370

191.

486

4−(phenylethynyl)benzaldehyde (3d)

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8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.37

4

7.15

27.

171

7.26

47.

332

7.34

87.

361

7.42

27.

441

7.51

97.

532

7.53

7

2.93

3

2.10

53.

043

2.00

02.

055

1−methyl−4−(phenylethynyl)benzene (3e)

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140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

21.5

12

76.7

1777

.035

77.3

53

88.7

3589

.577

120.

205

123.

496

128.

079

128.

323

129.

126

131.

510

131.

557

138.

390

1−methyl−4−(phenylethynyl)benzene (3e)

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8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.83

3

6.87

16.

892

7.26

17.

308

7.32

17.

339

7.35

37.

463

7.48

47.

505

7.52

07.

524

3.00

3

2.00

0

3.03

14.

053

1−methoxy−4−(phenylethynyl)benzene (3f)

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160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm55

.294

76.6

8076

.998

77.3

15

88.0

4489

.341

113.

984

115.

375

123.

583

127.

913

128.

288

131.

435

133.

038

159.

604

1−methoxy−4−(phenylethynyl)benzene (3f)

ESI - 34

Page 35: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.00

67.

016

7.02

87.

261

7.28

67.

299

7.34

07.

344

7.35

27.

355

7.37

97.

509

7.51

37.

522

7.53

17.

545

1.00

01.

937

3.37

82.

366

2−(phenylethynyl)thiophene (3g)

ESI - 35

Page 36: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

76.6

9277

.009

77.3

27

82.5

92

93.0

11

122.

922

123.

324

127.

084

127.

233

128.

362

128.

406

129.

203

131.

408

131.

880

132.

499

2−(phenylethynyl)thiophene (3g)

ESI - 36

Page 37: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.25

97.

369

7.39

77.

417

7.43

67.

503

7.52

27.

555

7.56

37.

663

7.68

17.

700

4.08

43.

078

2.00

0

1−(phenylethynyl)−2−(tri�uoromethyl)benzene (3h)

ESI - 37

Page 38: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−170−160−150−140−130−120−110−100−90−80−70−60−50−40−30−20−1010 0 ppm

−62.

704

1−(phenylethynyl)−2−(tri�uoromethyl)benzene (3h)

ESI - 38

Page 39: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 ppm

76.6

7676

.994

77.3

11

85.3

39

94.9

19

121.

590

122.

242

122.

733

124.

960

125.

812

125.

862

125.

911

125.

961

127.

891

128.

378

128.

800

131.

372

131.

691

133.

692

1−(phenylethynyl)−2−(tri�uoromethyl)benzene (3h)

ESI - 39

Page 40: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.25

97.

471

7.49

07.

509

7.54

77.

566

7.58

47.

670

7.69

07.

709

7.73

18.

215

8.23

7

1.11

81.

093

4.14

2

2.00

0

1−((4−nitrophenyl)ethynyl)−2−(tri�uoromethyl)benzene (3i)

ESI - 40

Page 41: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−170−160−150−140−130−120−110−100−90−80−70−60−50−40−30−20−1010 0 ppm

−62.

626

1−((4−nitrophenyl)ethynyl)−2−(tri�uoromethyl)benzene (3i)

ESI - 41

Page 42: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

77.1

3877

.456

77.7

73

90.6

3692

.996

120.

687

122.

504

124.

087

125.

253

126.

452

126.

501

126.

550

126.

598

129.

446

129.

939

132.

036

132.

831

134.

365

147.

746

1−((4−nitrophenyl)ethynyl)−2−(tri�uoromethyl)benzene (3i)

ESI - 42

Page 43: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.62

4

7.26

07.

442

7.46

17.

480

7.53

17.

550

7.56

97.

624

7.64

47.

684

7.70

27.

721

7.94

97.

969

2.97

2

1.21

21.

304

2.10

62.

193

2.00

0

1−(4−((2−(tri�uoromethyl)phenyl)ethynyl)phenyl)ethanone (3j)

ESI - 43

Page 44: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−170−160−150−140−130−120−110−100−90−80−70−60−50−40−30−20−1010 0 ppm

−62.

699

1−(4−((2−(tri�uoromethyl)phenyl)ethynyl)phenyl)ethanone (3j)

ESI - 44

Page 45: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

26.6

74

76.7

1977

.036

77.3

53

88.3

97

93.8

59

120.

880

122.

161

124.

879

125.

933

125.

981

126.

030

126.

078

127.

507

128.

289

128.

526

131.

516

131.

807

133.

856

136.

602

197.

330

1−(4−((2−(tri�uoromethyl)phenyl)ethynyl)phenyl)ethanone (3j)

ESI - 45

Page 46: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.38

2

7.16

87.

187

7.25

97.

380

7.39

97.

418

7.44

37.

463

7.49

07.

509

7.52

87.

647

7.66

87.

689

3.04

5

2.02

2

4.39

82.

000

1−(p−tolylethynyl)−2−(tri�uoromethyl)benzene (3k)

ESI - 46

Page 47: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−170−160−150−140−130−120−110−100−90−80−70−60−50−40−30−20−1010 0 ppm

−62.

654

1−(p−tolylethynyl)−2−(tri�uoromethyl)benzene (3k)

ESI - 47

Page 48: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

21.5

44

76.6

9277

.010

77.3

27

84.7

98

95.2

40

119.

681

121.

820

122.

298

125.

015

125.

786

125.

834

125.

882

125.

928

127.

686

129.

159

131.

351

131.

600

133.

610

139.

068

1−(p−tolylethynyl)−2−(tri�uoromethyl)benzene (3k)

ESI - 48

Page 49: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

3.83

8

6.88

46.

904

7.26

07.

367

7.38

57.

404

7.48

37.

503

7.63

07.

649

7.66

07.

680

2.98

9

2.00

0

1.01

42.

997

2.00

3

1−((4−methoxyphenyl)ethynyl)−2−(tri�uoromethyl)benzene (3l)

ESI - 49

Page 50: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−170−160−150−140−130−120−110−100−90−80−70−60−50−40−30−20−1010 0 ppm

−62.

867

1−((4−methoxyphenyl)ethynyl)−2−(tri�uoromethyl)benzene (3l)

ESI - 50

Page 51: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm55

.317

76.6

7776

.995

77.3

12

84.2

48

95.1

39

114.

050

114.

848

121.

945

122.

306

125.

024

125.

772

125.

817

125.

865

125.

917

127.

485

131.

327

133.

216

133.

447

160.

061

1−((4−methoxyphenyl)ethynyl)−2−(tri�uoromethyl)benzene (3l)

ESI - 51

Page 52: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.03

97.

050

7.06

07.

260

7.34

97.

360

7.39

77.

416

7.43

67.

500

7.51

97.

537

7.64

77.

666

7.68

57.

704

1.00

01.

950

1.05

81.

065

2.07

0

2−((2−(tri�uoromethyl)phenyl)ethynyl)thiophene (3m)

ESI - 52

Page 53: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−170−160−150−140−130−120−110−100−90−80−70−60−50−40−30−20−1010 0 ppm

−62.

721

2−((2−(tri�uoromethyl)phenyl)ethynyl)thiophene (3m)

ESI - 53

Page 54: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

76.7

2977

.046

77.3

63

88.2

7189

.089

121.

229

122.

229

122.

627

124.

947

125.

854

125.

905

125.

954

126.

002

127.

248

128.

028

128.

162

131.

432

132.

682

133.

429

2−((2−(tri�uoromethyl)phenyl)ethynyl)thiophene (3m)

ESI - 54

Page 55: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

−1.5−1.0−0.58.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.89

10.

909

0.92

51.

317

1.32

61.

335

1.34

41.

418

1.43

51.

454

1.47

21.

491

1.58

51.

603

1.62

31.

641

1.65

82.

426

2.44

42.

461

7.26

17.

499

7.52

1

8.13

78.

159

3.60

5

4.14

32.

458

2.42

4

2.28

5

2.00

5

2.00

0

1-nitro-4-(oct-1-ynyl)benzene (3n)

ESI - 55

Page 56: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

14.0

18

19.5

5022

.511

28.3

5228

.585

31.2

83

76.6

7376

.992

77.3

0879

.286

96.8

13

123.

465

131.

223

132.

214

146.

560

1−nitro−4−(oct−1−ynyl)benzene (3n)

ESI - 56

Page 57: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.88

90.

906

0.92

21.

323

1.33

21.

418

1.43

51.

453

1.47

11.

490

1.59

51.

614

1.63

31.

650

2.40

92.

427

2.44

42.

584

7.26

17.

448

7.46

8

7.86

07.

881

3.35

8

4.60

72.

192

2.33

0

1.97

83.

097

1.92

5

2.00

0

1−(4−(oct−1−yn−1−yl)phenyl)ethanone (3o)

ESI - 57

Page 58: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

14.0

2619

.522

22.5

2526

.552

28.5

1328

.589

31.3

13

76.6

7676

.994

77.3

1180

.079

94.4

49

128.

146

129.

176

131.

625

135.

633

197.

400

1−(4−(oct−1−ynyl)phenyl)ethanone (3o)

ESI - 58

Page 59: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.94

00.

958

0.97

61.

455

1.47

31.

492

1.51

01.

528

1.57

41.

592

1.61

11.

629

1.64

62.

433

2.45

02.

468

7.26

07.

496

7.51

8

8.13

38.

155

3.18

2

2.24

12.

590

2.06

7

2.02

3

2.00

0

1−(hex−1−yn−1−yl)−4−nitrobenzene (3p)

ESI - 59

Page 60: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

13.6

05

19.2

4122

.022

30.4

34

76.7

3777

.054

77.3

7379

.263

96.7

81

123.

465

131.

214

132.

225

146.

490

1−(hex−1−ynyl)−4−nitrobenzene (3p)

ESI - 60

Page 61: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.27

1

7.26

0

7.58

47.

605

8.15

98.

180

8.96

0

1.97

8

2.00

0

Trimethyl((4−nitrophenyl)ethynyl)silane (7q)

ESI - 61

Page 62: γ-Valerolactone as an alternative biomass-derived medium ... · page ESI 2-ESI 21 Full characterization data (1H NMR, 13C NMR, 19F NMR, EA, GC-EIMS) for Compounds 3 a-q ... value

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

−0.3

06

76.7

0177

.018

77.3

35

100.

618

102.

663

123.

481

129.

960

132.

686

147.

097

trimethyl((4−nitrophenyl)ethynyl)silane (3q)

ESI - 62