2
538
B. Hellbach et al.
PAPER
Trideca-1,12-diyne (10d)21,22
Octa-1,7-diyne (10i)11,24
Yield: 4.01 g (65%); colorless liquid.
Yield: 1.86 g (50%); colorless liquid.
–
1
IR (film): 3298, 2947, 2866, 2117, 1459, 636 cm–1.
IR (film): 3306, 2931, 2856, 2117, 1465, 628 cm .
1
= 2.17 (dt, 3
1H NMR (CDCl3): = 2.20 (dt, J
3
= 5.0 Hz, 4JH3H1/H6H8
= 2.7 Hz, 2 H, ≡CH), 1.67–
H NMR (CDCl ):
J
= 7.1 Hz,
= 2.6 Hz,
=
3
H3H4/H11H10
4
H3H4/H6H5
4
4
JH3H1/H11H13 = 2.6 Hz, 4 H, CH C≡), 1.93 (t, J
2.4 Hz, 4 H, CH C≡), 1.94 (t, J
2
H1H3/H13H11
2
H1H3/H8H6
2
1
H, ≡CH), 1.57–1.48 (m, 4 H, CH ), 1.41–1.37 (m, 4 H, CH ),
.32–1.23 (m, 6 H, CH2).
1.62 (m, 4 H, CH2).
13C NMR (CDCl3):
2
2
= 84.12 (C≡), 68.65 (≡CH), 27.47 (CH2),
13C NMR (CDCl3): = 84.87 (C≡), 68.20 (≡CH), 29.46 (CH2),
9.16 (CH ), 28.84 (CH ), 28.60 (CH ), 18.52 (CH C≡).
18.03 (CH C≡).
2
2
+
2
2
2
2
MS (CI): m/z = 107 (62) [M + H], 105 (70), 93 (46), 91 (100), 81
(32), 79 (88), 69 (37), 67 (35).
+
MS (CI): m/z = 177 (4) [M + H], 175 (12), 161 (11), 149 (10), 147
(
(
13), 135 (25), 133 (22), 121 (30), 109 (35), 107 (39), 95 (83), 81
100), 67 (24).
Methylated Dialkynes 11a–i; General Procedure
To a solution of the diyne 10a–i (10a: 4.4 g. 10b: 4.1 g, 10c: 3.8 g,
10d: 3.5 g, 10e: 3.3 g, 10f: 3.0 g, 10g: 2.7 g, 10h: 2.4 g, 10i: 2.1 g;
20.0 mmol) in anhyd THF (250 mL) at –70 °C was added 1.6 M n-
BuLi in hexane (28.1 mL, 45.0 mmol) under an Ar atmosphere. A
white precipitate was observed, and the color of the solution
changed to yellow after all n-BuLi had been added. The stirring was
continued for 1.5 h. Finally methyl iodide (3.1 mL, 50.0 mmol) was
added and the reaction mixture was allowed to warm to r.t. over-
night. The reaction was quenched by pouring it into 200 mL of wa-
ter as soon as the white precipitate had disappeared. The organic
layer was separated and the aq layer was extracted with petroleum
ether 30–40 (3 × 100 mL). The combined organic layers were con-
centrated in vacuo and traces of terminal acetylenes were removed
Dodeca-1,11-diyne (10e)22
Yield: 2.67 g (47%); colorless solid; mp 27 °C.
–
1
IR (KBr): 3301, 2934, 2857, 2118, 1465, 631 cm .
1
3
= 7.2 Hz, 4JH3H1/H10H12
H NMR (CDCl ): = 2.15 (dt, J
=
3
H3H4/H10H9
= 2.6 Hz, 2 H, ≡CH),
H1H3/H12H10
4
2
1
.6 Hz, 4 H, CH C≡), 1.91 (t, J
2
.53–1.46 (m, 4 H, CH ), 1.39–1.34 (m, 4 H, CH ), 1.30–1.24 (m, 4
2
2
H, CH2).
13C NMR (CDCl3): = 84.76 (C≡), 68.21 (≡CH), 29.08 (CH2),
2
8.81 (CH ), 28.58 (CH ), 18.51 (CH -C≡).
2 2 2
+
MS (CI): m/z = 163 (8) [M + H], 161 (20), 149 (13), 147 (21), 135
(
(
22), 133 (30), 121 (46), 119 (28), 109 (22), 107 (41), 95 (56), 93
38), 81 (100), 67 (10).
by washing with a solution of Cu(I)Cl in aq NH (150 mL). After
3
separation of the organic layers, the aq layer was extracted with pe-
troleum ether 30–40 (4 × 50 mL) and the combined organic layers
were dried over Na SO , filtered, and evaporated. The residue was
Undeca-1,10-diyne (10f)22
Yield: 4.0 g (77%); colorless liquid.
2
4
purified by flash chromatography (petroleum ether, bp 30–40 °C).
–
1
IR (film): 3300, 2935, 2859, 2117, 1464, 632 cm .
1H NMR (CDCl3): = 2.17 (dt, J
3
= 7.4 Hz, 4J
=
H3H1/H9H11
Octadeca-2,16-diyne (11a)
Yield: 3.99 g (81%); colorless solid.
H3H4/H9H8
= 2.7 Hz, 2 H, ≡CH),
H1H3/H11H9
4
2
.7 Hz, 4 H, CH C≡), 1.93 (t, J
2
–
1
1
.56–1.48 (m, 4 H, CH ), 1.44–1.36 (m, 4 H, CH ), 1.35–1.27 (m, 2
IR (KBr): 2919, 2850, 1629, 1470, 719 cm .
2
2
H, CH2).
1
H NMR (CDCl3):
JH1H4/H18H15 = 2.5 Hz, 6 H, ≡CCH ), 1.49–1.40 (m, 4 H, CH ), 1.38–
= 2.12–2.06 (m, 4 H, CH C≡), 1.78 (t,
2
13C NMR (CDCl3): = 84.77 (-C≡), 68.26 (≡CH), 28.70 (CH2),
8.52 (CH ), 18.49 (CH -C≡), 2 methylene signals fall together.
5
3
2
2
1.31 (m, 4 H, CH ), 1.30–1.21 (m, 12 H, CH ).
2
2
2
2
+
13C NMR (CDCl3): = 79.57 (CH C≡), 75.43 (≡CCH ), 29.73
MS (CI): m/z = 149 (15) [M + H], 135 (29), 133 (32), 121 (33), 109
43), 107 (68), 95 (55), 93 (61), 81 (100), 79 (28), 67 (22).
2
3
(
(CH ), 29.69 (CH ), 29.34 (CH ), 29.26 (CH ), 29.07 (CH ), 18.88
2 2 2 2 2
(
CH C≡), 3.61 (≡CCH ).
2 3
Deca-1,9-diyne (10g)11
Yield: 2.44 g (52%); colorless liquid.
+
+
MS (EI): m/z = 246 (1) [M ], 231 (11) [M – CH ], 217 (6), 203 (5),
1
95 (100), 81 (63), 67 (48), 55 (31), 41 (19).
3
89 (6), 175 (12), 161 (24), 147 (33), 133 (37), 121 (52), 107 (69),
–
1
IR (film): 3299, 2938, 2861, 2117, 1463, 633 cm .
1H NMR (CDCl3): = 2.18 (dt, J
3
= 7.2 Hz, 4JH3H1/H8H10
= 2.6 Hz, 2 H, ≡CH),
=
H3H4/H8H7
HRMS: m/z calcd for C H : 246.2347; found: 246.2338.
18 30
4
2
1
.6 Hz, 4 H, CH C≡), 1.93 (t, J
2
H1H3/H10H8
.54–1.50 (m, 4 H, CH ), 1.44–1.39 (m, 4 H, CH ).
Heptadeca-2,15-diyne (11b)
2
2
13C NMR (CDCl3): = 84.66 (-C≡), 68.32 (≡CH), 28.42 (CH2),
Yield: 4.23 g (91%); colorless solid; mp 47–48 °C;.
–
1
2
8.30 (CH ), 18.47 (CH -C≡).
IR (KBr): 2927, 2851, 1632, 1464, 725 cm .
1H NMR (CDCl3): = 2.13–2.07 (m, 4 H, CH C≡), 1.77 (t, J
2
2
+
5
MS (CI): m/z = 135 (60) [M + H,] 60), 121 (45), 119 (68), 109 (21),
07 (42), 95 (98), 93 (77), 81 (100), 79 (30), 69 (16), 67 (22).
2
H1H4/
1
= 2.5 Hz, 6 H, ≡CCH ), 1.51–1.42 (m, 4 H, CH ), 1.37–1.32
H17H14
3
2
(
m, 4 H, CH ), 1.31–1.23 (m, 10 H, CH ).
2 2
Nona-1,8-diyne (10h)11,23
Yield: 2.23 g (53%); colorless liquid.
13C NMR (CDCl3):
CH ), 29.67 (CH ), 29.32 (CH ), 29.25 (CH ), 29.06 (CH ), 18.88
= 79.56 (CH C≡), 75.43 (≡CCH ), 29.72
2 3
(
2
2
2
2
2
–
1
IR (film): 3298, 2941, 2863, 2117, 1464, 635 cm .
(CH C≡), 3.60 (≡CCH ).
2
3
1
3
= 6.64 Hz, 4JH3H1/H7H9
= 2.6 Hz, 2 H, ≡CH), 1.57–
+
+
H NMR (CDCl ): = 2.19 (dt, J
=
MS (EI): m/z = (1) 232 [M ], 217 (12) [M – CH ], 203 (9), 189 (9),
3
H3H4/H7H6
3
4
2
1
.4, 4 H, CH C≡), 1.93 (t, J
175 (25), 161 (33), 147 (39), 133 (47), 121 (54), 107 (89), 95 (100),
81 (90), 67 (65), 55 (46), 41 (39).
2
H1H3/H9H7
.49 (m, 6 H, CH2).
13C NMR (CDCl3): = 84.49 (C≡), 68.43 (≡CH), 28.09 (CH2),
7.96 (CH ), 18.42 (CH C≡).
HRMS: m/z calcd for C H : 232.2191; found: 232.2136.
17
28
2
2
2
Anal. Calcd for C H : C, 87.86; H, 12.14. Found: C, 87.65; H,
1
7
28
+
MS (CI): m/z = 121 (14) [M + H], 119 (18), 109 (7), 107 (19), 93
60), 91 (58), 83 (21), 81 (58), 79 (100), 69 (53), 67 (46).
12.05.
(
Synthesis 2003, No. 16, 2535–2541 © Thieme Stuttgart · New York