Arkivoc 2020, vii, 0-0
Lücke, A.-L. et al.
2-Methyl-4-(thiophen-3-yl)but-3-yn-2-ol (11).40 Samples of 0.400 g (2.46 mmol) of 1-bromothiophene and 0.6
mL (6.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was performed with petroleum
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ether : ethyl acetate = 2 : 1. Yellowish solid. H-NMR (400 MHz, CDCl3): δ 7.33 (d, JH,H 7.8 Hz, 1 H), 7.18-7.15
(m, 1 H), 7.01 (d, JH,H 7.8 Hz, 1 H), 2.19 (br s, 1 H), 1.53 (s, 6 H), ppm.
Methyl 4-(3-hydroxy-3-methylbut-1-yn-1-yl)benzoate (12).37 Samples of 1.00 g (4.65 mmol) of methyl-4-
bromobenzoate and 1.2 mL (12.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was
performed with petroleum ether : ethyl acetate = 2:1. Yellowish solid. 1H-NMR (400 MHz, CDCl3): δ 8.01-7.97
(m, 2 H), 7.50-7.46 (m, 2 H), 3.91 (s, 3 H), 2.29 (s, 1 H), 1.63 (s, 6 H) ppm.
2-Methyl-4-(naphth-1-yl)but-3-yn-2-ol (13).37 Samples of 0.500 g (2.41 mmol) of 1-bromonaphthalene and 0.6
mL (6.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was performed with petroleum
ether : ethyl acetate = 2 : 1. Brownish solid. 1H-NMR (400 MHz, CDCl3): δ 8.28 (d, JH,H 7.8 Hz, 1 H) ), 7.80-7.74
(m, 2 H), 7.60 (d, JH,H 7.8 Hz, 1 H), 7.55-7.52 (m, 1 H ), 7.48-7.44 (m, 1 H), 7.36-7.33 (m, 1 H), 2.72 (br s, 1 H),
1.71 (s, 6 H) ppm.
4-(3,5-Dimethylphenyl)-2-methylbut-3-yn-2-ol (14).39 Samples of 0.500 g (2.70 mmol) of 1-bromo-3,5-
dimethylbenzene and 0.6 mL (6.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was
performed with petroleum ether : ethyl acetate = 4 : 1. Brownish solid. 1H-NMR (400 MHz, CDCl3): δ 7.04 (s, 2
H), 6.93 (s, 1 H), 2.27 (s, 6 H), 2.27 (br s, 1 H),1.60 (s, 6 H) ppm.
2-Methyl-4-(quinolin-2-yl)but-3-yn-2-ol (15).44 Samples of 0.500 g (2.40 mmol) of 2-bromoquinoline and 0.6
mL (6.0 mmol) of 2--methyl-but-3-yn-2-ol were used. Column chromatography was performed with petroleum
ether : ethyl acetate = 2 : 1. Brownish solid. 1H-NMR (400 MHz, CDCl3): δ 9.07-9.06 (m, 1 H), 8.15-8.10 (m, 2 H),
7.72-7.66 (m, 2 H), 7.54-7.50 (m, 1 H), 5.58 (br. s, 1 H), 1.69 (s, 6 H) ppm.
2-Methyl-4-(phenanthren-9-yl)but-3-yn-2-ol (16).49 Samples of 0.500 g (1.95 mmol) of 9-bromophenanthrene
and 0.6 mL (6.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was performed with
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petroleum ether : ethyl acetate = 2 : 1. Brownish solid. H-NMR (400 MHz, CDCl3): δ 8.70-8.64 (m, 3 H) 8.40-
8.38 (m, 1 H), 7.98 (s, 1 H), 7.85-7.83 (m, 2 H), 7.70-7.66 (m, 1 H), 7.65-7.60 (m, 1 H), 2.00 (br s, 1 H), 1.76 (s, 6
H) ppm.
2-Methyl-4-(pyridin-3-yl)but-3-yn-2-ol (17).37 Samples of 0.500 g (3.16 mmol) of 3-bromopyridine and 0.6 mL
(6.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was performed with petroleum
ether : ethyl acetate = 5 : 1. Brownish solid. 1H-NMR (400 MHz, CDCl3): δ 8.76-8.73 (m, 1 H), 8.52-8.49 (m, 1 H),
7.75-7.70 (m, 1 H), 7.26-7.21 (m, 1 H), 3.92 (br. s, 1 H), 1.61 (s, 6 H) ppm.
4-(Anthracen-9-yl)-2-methylbut-3-yn-2-ol (18).50 Samples of 0.500 g (1.95 mmol) of 9-bromoanthracene and
0.6 mL (6.0 mmol) of 2-methyl-but-3-yn-2-ol were used. Column chromatography was performed with
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petroleum ether : ethyl acetate = 2 : 1. Yellowish solid. H-NMR (400 MHz, CDCl3): δ 8.48 (d, JH,H 8.6 Hz, 2 H),
8.41 (s, 1 H), 7.98 (d, JH,H 8.6 Hz, 2 H), 7.58-7.55 (m, 2 H), 7.51-7.47 (m, 2H), 2.30 (br s, 1H), 1.85 (s, 6 H), ppm.
4,4‘-([1,1‘-Biphenyl]-4,4‘-diyl)bis-(2-methylbut-3-yn-2-ol) (19).44 Samples of 0.200 g (0.64 mmol) of 4,4'-
dibromo-1,1'-biphenyl and 0.3 mL (3.0 mmol) of 2--methyl-but-3-yn-2-ol were used. Column chromatography
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was performed with petroleum ether : ethyl acetate = 8 : 1. Brownish solid. H-NMR (400 MHz, DMSO-d6): δ
7.70 (d, JH,H 8.4 Hz, 4 H), 7.48 (d, JH,H 8.4 Hz, 4 H), 5.51 (bs, 2 H), 1.49 (s, 12 H), ppm.
General Procedure for the preparation of compounds 20-23.
Under an inert atmosphere (N2) the halogen compound was dissolved in 20 ml of dry toluene and 10 mol-% of
the corresponding catalyst was added. After stirring the mixture for 10 min at rt 0.075 g (0.4 mmol)
diphenylamine and 0.424 g (2.0 mmol) potassium phosphate (K3PO4) were added. Then the mixture was
stirred at 100 °C for 12 h. After cooling the mixture to room temperature, the solvent was removed under
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