PAPER
Homo- and Heterocoupling of Terminal Alkynes
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1H NMR (500 MHz, CDCl3): d = 8.20 (dd, J = 7.8, 1.8 Hz, 2 H),
8.07 (br s, 2 H), 7.45 (td, J = 7.8, 1.8 Hz, 2 H), 7.07 (t, J = 7.8 Hz,
2 H), 6.97 (d, J = 8.3 Hz, 2 H), 4.34 (d, J = 5.1 Hz, 4 H), 3.98 (s, 6
H).
13C NMR (125.7 MHz, CDCl3): d = 164.9, 157.5, 133.2, 132.4,
121.3, 120.6, 111.3, 74.6, 67.3, 56.0, 29.9.
13C NMR (125.7 MHz, CDCl3): d = 165.7, 133.4, 129.8, 129.2,
128.4, 84.0, 73.5, 70.6, 66.2, 65.5, 52.8, 30.9.
HRMS (EI): m/z [M + Na]+ calcd for C15H14O3Na: 265.0841; found:
265.0848.
Acknowledgment
HRMS (EI): m/z [M + H]+ calcd for C22H21N2O4: 377.1501; found:
377.1494.
This work was supported by Department of Science & Technology,
Government of India, New Delhi (Grant No. SR/S1/OC-60/2006).
We thank the Sophisticated Analytical Instruments Facility (SAIF)
and the Department of Chemistry, IIT Madras, for the analytical da-
ta. K.B. thanks University Grants Commission, New Delhi for a re-
search fellowship.
Unsymmetric 1,3-Diynes 3 under Atmospheric Air; General
Procedure
A mixture of alkyne X (1 mmol), alkyne Y (5 mmol), piperidine (3
mmol), and Cu(OAc)2·H2O (10 mol%) in CH2Cl2 (5 mL) was stirred
in open atmospheric air at 25 °C (TLC monitoring) for 3–10 h. The
mixture was concentrated in vacuo and the residue was purified by
column chromatography (silica gel, PE–EtOAc) to afford 3.
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N-(5-Phenylpenta-2,4-diynyl)benzamide (3e)
Mp 106–108 °C; Rf = 0.2 (hexanes–EtOAc, 9:1).
IR (neat): 3353, 3067, 2978, 2244, 1763, 1634, 1435, 1044, 755,
689 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.25 (br s, 1 H), 8.04–7.89 (m, 2
H), 7.5–7.30 (m, 8 H), 4.36 (d, J = 5.1 Hz, 2 H).
13C NMR (125.7 MHz, CDCl3): d = 167.0, 133.7, 132.3, 131.4,
129.5, 129.1, 128.3, 128.2, 127.3, 79.7, 76.7, 73.6, 67.1, 30.0.
HRMS (EI): m/z [M + H]+ calcd for C18H14NO: 260.1075; found:
260.1070.
2-Fluoro-N-(5-phenylpenta-2,4-diynyl)benzamide (3f)
Mp 86–88 °C; Rf = 0.1 (hexanes–EtOAc, 9:1).
IR (neat): 3460, 3053, 2971, 2843, 2544, 2213, 2148, 1719, 1660,
1527, 1295, 1030, 752 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.12 (td, J = 7.9, 1.9 Hz, 1 H),
7.49–7.47 (m, 3 H), 7.36–7.26 (m, 4 H), 7.16–7.11 (m, 1 H), 6.98
(br s, 1 H), 4.45 (dd, J = 5.2, 1.2 Hz, 2 H).
13C NMR (125.7 MHz, CDCl3): d = 162.9, 160.6, 133.7, 132.4,
130.1, 129.3, 128.4, 124.9, 121.3, 120.1, 116.0, 78.0, 77.3, 73.3,
68.2, 30.5.
HRMS (EI): m/z [M + H]+ calcd for C18H13FNO: 278.0981; found:
278.0985.
2-Methoxy-N-(5-phenylpenta-2,4-diynyl)benzamide (3g)
Mp 120–122 °C; Rf = 0.1 (hexanes–EtOAc, 9:1).
IR (neat): 3384, 3055, 2978, 2936, 2244, 1893, 1649, 1526, 1245,
1025, 753 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.20 (dd, J = 7.8, 1.8 Hz, 1 H),
8.10 (br s, 1 H), 7.47–7.43 (m, 3 H), 7.35–7.27 (m, 3 H), 7.06 (t,
J = 7.6 Hz, 1 H), 6.96 (d, J = 8.1 Hz, 1 H), 4.42 (d, J = 5.2 Hz, 2 H),
3.97 (s, 3 H).
13C NMR (125.7 MHz, CDCl3): d = 164.9, 157.5, 133.2, 132.5,
132.4, 129.2, 128.3, 121,4, 121.3, 120.6, 111.3, 79.0, 77.0, 73.5,
67.6, 56.0, 30.2.
HRMS (EI): m/z [M + H]+ calcd for C19H16NO2: 290.1181; found:
290.1173.
6-Hydroxy-6-methylhepta-2,4-diynyl Benzoate (3h)
Rf = 0.1 (hexanes–EtOAc, 9:1).
IR (neat): 3461, 3322, 3063, 2983, 2935, 2211, 1721, 1602, 1444,
1262, 1101, 956, 832, 711 cm–1.
1H NMR (500 MHz, CDCl3): d = 8.06–8.04 (m, 2 H), 7.59–7.56 (m,
1 H), 7.45 (t, J = 7.1 Hz, 2 H), 4.98 (s, 2 H), 1.53 (s, 6 H).
Synthesis 2010, No. 20, 3461–3466 © Thieme Stuttgart · New York