Upload
others
View
4
Download
0
Embed Size (px)
Citation preview
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
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
ESI - 2
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)
ESI - 3
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)
ESI - 4
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
ESI - 5
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
ESI - 6
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
ESI - 7
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
ESI - 8
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)
ESI - 9
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
ESI - 10
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)
ESI - 11
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
ESI - 12
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)
ESI - 13
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)
ESI - 14
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)
ESI - 15
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)
ESI - 16
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)
ESI - 17
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)
ESI - 18
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)
ESI - 19
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)
ESI - 20
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)
ESI - 21
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)
ESI - 22
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)
ESI - 23
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)
ESI - 24
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)
ESI - 25
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
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)
ESI - 27
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
ESI - 28
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)
ESI - 29
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)
ESI - 30
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)
ESI - 31
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)
ESI - 32
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)
ESI - 33
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
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
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
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
−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
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
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
−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
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
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
−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
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
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
−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
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
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
−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
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
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
−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
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
−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
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
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
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
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
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
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
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