Perylene-Substituted Organotrialkynyltin Compounds
Organometallics, Vol. 22, No. 22, 2003 4591
126.8 (C8 11), 124.7 (C2), 124.0 (C4), 120.7 (C6
12)),
and 1 and (7 or
amber waxy solid. Yield: 3.6 g (95%). 1H NMR (250 MHz,
CDCl3, 293 K): δ 8.18 (d, 7.8, 1H, H6), 8.16 (d, 7.8, 1H, H12),
8.12 (d, 7.8, 1H, H7), 8.09 (d, 7.8, 1H, H1), 7.86 (d, 8.3, 1H,
H4), 7.64 (d, 8.3, 1H, H9 10), 7.63 (d, 8.3, 1H, H9 10), 7.49
or
120.4 (C7 or 12), 32.8 ([17], Cb), 29.7 ([56], Cc), 27.6 ([6], Cd), 26.4
([330], Ca). 119Sn NMR (74.6 MHz, CDCl3, 293 K): δ -98.5 (â),
-100.1 (R). UV-visible (CH2Cl2; λmax, nm (ꢀ, L mol-1 cm-1)):
259 (39 600), 409 (14 500), 434 (29 300), 459 (34 400). MS-EI
(m/z): 646 (5%) [M+], 563 (32%) [M+ - C6H11], 278 (100%) [M+
or
or
(dd, 8.3 and 7.8, 1H, H5), 7.45 (dd, 8.3 and 7.8, 1H, H8 11),
or
7.44 (dd, 8.3 and 7.8, 1H, H8 11), 7.32 (d, 7.8, 1H, H2), 3.00
or
- Sn(C6H11)3], 426 (5%) [M+ - Sn(C6H11)3], 309 (48%) [M+
-
(apparent triplet, 2H, H13), 2.19 (m, [131], 6H, Hc), 1.82 (m,
[96], 4H, H14,17), 1.44 (m, 6H, Hd), 1.33 (m, 6H, He), 1.28 (t,
7.60, [72], 2H, H18), 0.82 (t, 7.32, 9H, Hf). 13C NMR (62.9 MHz,
CDCl3, 293 K): δ 137.5 (C3), 133.6, 132.3, 130.7, 130.5, 130.4,
Sn(C6H11)3], 265 (100%) [M+ - Sn(C6H11)3C3H6]. HRMS-EI:
found (calcd) 646.2632 (646.2621). Anal. Found (calcd for
C
42H52Sn): C, 74.7 (74.4); H, 7.4 (7.2).
128.4, 128.0, 127.5, 126.6 (C9 10), 126.3 (C8 10), 125.7 (C2),
3-(4-(Tr ich lor ostan n yl)bu tyl)per ylen e (2a). In a Schlenk
or
or
125.6 (C11 or 8), 126.5 (C11 or 8), 125.2 (C5), 122.8 (C4), 119.0 (3C,
C6 12)), 118.6 (C7 12), 111.3 ([156], Cb), 76.3 ([804],
tube under a nitrogen atmosphere at room temperature, 1.61
g (6.2 mmol) of tin tetrachloride was added dropwise to a
solution of 3a (4.2 g, 6.2 mmol) in CH2Cl2 (100 mL). The
stirring was then continued for a further 24 h. After evapora-
tion of the solvent, the residue was washed with n-pentane (6
× 50 mL) in order to remove the tricyclohexyltin chloride
formed. After drying under vacuum at 70 °C for 3 days, a
yellow greenish powder of 2a was isolated. Yield: 3.1 g (95%).
This compound had to be stored under nitrogen with light
and
1
et (7 or
or
Ca), 33.6 (C14), 32.9 (C13), 30.6 ([8], Cd), 25.8 ([29], C17), 21.9
(Ce), 19.8 ([15], Cc), 15.2 ([601], C18), 13.6 (Cf). 119Sn NMR (74.6
MHz, CDCl3, 293 K): δ -249.8. UV-visible (CH2Cl2; λmax, nm
(ꢀ, L mol-1 cm-1)): 228 (18 600), 256 (30 600), 395 (11 500),
417 (24 200), 445 (31 700). MS-EI (m/z): 670 (25%) [M+], 614
(8%) [M+ - C4H9], 588 (34%) [M+ - C6H9], 278 (100%) [M+
-
Sn(C6H9)3C2H4]. HRMS-EI: found (calcd) 670.2627 (670.2621).
Anal. Found (calcd for C42H46Sn): C, 74.0 (75.3); H, 6.9 (6.9);
Sn, 17.8 (17.7).
1
exclusion. Mp: 120 °C. H NMR (250 MHz, CDCl3, 293 K): δ
8.21 (d, 7.9, 1H, H6), 8.18 (d, 7.3, 1H, H12), 8.15 (d, 7,9, 1H,
H7), 8.11 (d, 7.8, 1H, H1), 7.81 (d, 7.9, 1H, H4), 7.66 (d, 8.3,
1H, H9 10), 7.64 (d, 8,3, 1H, H9 10), 7.51 (dd, 7.9 and 7.9,
3-(6-(Tr ih ex-1-yn ylsta n n yl)h exyl)p er ylen e (1b). 1b was
formed by a procedure analogous with that for 1a with 2b (3.1
g, 5.5 mmol), n-butyllithium 2.5 M in hexanes (8.1 mL, 20.2
mmol), and hex-1-yne (1.8 g, 21.9 mmol) in anhydrous THF
(60 mL). After filtration over MgSO4, evaporation of the
solvent, and drying under vacuum, an amber waxy solid was
or
or
1H, H5), 7.47 (dd, 8.3 and 7.9, 1H, H8 11), 7.44 (dd, 8.3 and
or
7.9, 1H, H8 11), 7.30 (d, 7.8, 1H, H2), 3.08 (apparent triplet,
or
2H, H13), 2.34 (apparent triplet, [84], H18), 2.10-1.90 (m, 4H,
H
14,17). 119Sn NMR (74.6 MHz, CDCl3, 293 K): δ +3.9. UV-
visible (CH2Cl2; λmax, nm (ꢀ, L mol-1 cm-1)): 228 (33 200), 256
(37 000), 396 (12 100), 417 (25 700), 444 (33 100). MS-EI (m/
z): 532 (16%) [M+], 306 (65%) [M+ - SnCl3], 265 (100%) (M+
- SnCl3C3H6]. HRMS-EI: found (calcd) 531.9574 (531.9584).
Anal. Found (calcd for C24H19Cl3Sn): C, 54.5 (54.1); H, 3.6 (3.6);
Cl, 19.8 (20.0).
1
isolated. Yield: 3.4 g (90%). H NMR (250 MHz, CDCl3, 293
K): δ 8.20 (d, 7.8, 1H, H6), 8.17 (d, 7.8, 1H, H12), 8.14 (d, 7.8,
1H, H7), 8.10 (d, 7.8, 1H, H1), 7.86 (d, 8.3, 1H, H4), 7.65 (d,
8.3, 1H, H9 10), 7.63 (d, 8.3, 1H, H9 10), 7.49 (dd, 8.3 and
or
or
7.8, 1H, H5), 7.45 (dd, 8.3 and 7.8, 1H, H8 11), 7.44 (dd, 8.3
or
and 7.8, 1H, H8 11), 7.32 (d, 7.8, 1H, H2), 2.97 (apparent
or
triplet, 2H, H13), 2.18 (t, 7.10, [131], 6H, Hc), 1.72 (m, 2H, H14),
1.66 (m, 2H, H17), 1.44 (m, 10H, Hd H15,16), 1.34 (m, 6H, He),
1.20 (t, 7.60, [76], 2H, H18), 0.82 (m, 9H, Hf). 13C NMR (62.9
MHz, CDCl3, 293 K): δ 138.6 (C3), 134.4, 132.8 (C3-C-C4),
3-(6-(Tr ich lor ost a n n yl)h exyl)p er ylen e (2b ). 2b was
formed by a procedure analogous with that for 2a with 3b (1.9
g, 2.7 mmol) and tin tetrachloride (0.7 g, 2.7 mmol) in CH2Cl2
(60 mL). After evaporation of the solvent, washing with
n-pentane, and drying under vacuum, a yellow greenish
powder of 2b was isolated. Yield: 1.5 g (98%). This compound
had to be stored under nitrogen with light exclusion. Mp: 125
°C. 1H NMR (250 MHz, CDCl3, 293 K): δ 8.19 (d, 7.1, 1H, H6),
8.16 (d, 7.1, 1H, H12), 8.13 (d, 7.1, 1H, H7), 8.09 (d, 7.8, 1H,
131.5, 131.3, 131.2, 129.2, 128.9, 128.3, 127.5 (C9 10), 127.1
or
(C9 10), 126.5 (C2), 126.4 (C11 8), 126.3 (C11 8), 126.0 (C5),
or
or
or
123.6 (C4), 119.9 (3C, C6
12)), 119.4 (C7 12), 112.0
and
1
and (7 or
or
([150], Cb), 77.2 ([846], Ca), 33.5 (C13), 33.0 (C15 or 16), 30.8 (Cd),
30.6 (C14), 29.5 (C15 16), 25.7 ([31], C17), 22.1 (Ce), 20.0 ([7],
or
Cc), 15.7 ([655], C18), 13.8 (Cf). 119Sn NMR (74.6 MHz, CDCl3,
293 K): δ -250.0. UV-visible (CH2Cl2; λmax, nm (ꢀ, L mol-1
cm-1)): 228 (15 500), 256 (28 000), 395 (10 000), 417 (21 000),
H1), 7.83 (d, 7.8 Hz, 1H, H4), 7.65 (d, 8.3, 1H, H9 10), 7.64 (d,
or
7.1, 1H, H9 10), 7.49 (dd, 7.8 and 7.1, 1H, H5), 7.45 (dd, 8.3
or
and 7.1, 1H, H8 11), 7.44 (dd, 8.3 and 7.1, 1H, H8 11), 7.30
or
or
445 (27 000). MS-EI (m/z): 698 (25%) [M+], 616 (15%) [M+
-
(d, 7.8, 1H, H2), 2.99 (apparent triplet, 2H, H13), 2.33 (apparent
triplet, [90], 2H, H18), 1.83-1.68 (m, 2H, H17), 1.60-1.40 (m,
4H, H14,15,16). 13C NMR (62.9 MHz, CDCl3, 293 K): δ 138.3,
134.6, 133.0, 132.9, 131.8, 131.4, 129.6, 128.5, 127.7, 127.4,
126.8, 126.6, 126.5, 126.3, 123.6, 120.2, 120.1, 120.0 (2C),
119.7, 30.5, 30.3, 29.7, 27.4, 26.2, 22.2. 119Sn NMR (74.6 MHz,
CDCl3, 293 K): δ +4.3. UV-visible (CH2Cl2; λmax, nm (ꢀ, L
mol-1 cm-1)): 228 (24 600), 256 (29 100), 396 (8900), 417
(20 000), 444 (25 900). MS-EI (m/z): 560 (9%) [M+], 336 (39%)
[M+ - SnCl3], 265 (100%) [M+ - SnCl3C5H10]. HRMS-EI:
found (calcd) 559.9887 (559.9865). Anal. Found (calcd for
C4H9], 363 (5%) [M+ - Sn(C4H9)3], 334 (60%) [M+ - Sn-
(C6H9)3C2H4], 265 (100%) [M+ - Sn(C6H9)3C5H10]. HRMS-EI:
found (calcd) 698.2978 (698.2934). Anal. Found (calcd for
C
42H46Sn): C, 74.5 (75.7); H, 7.2 (7.2); Sn, 17.6 (17.0).
3-(2-(Tr ih ex-1-yn ylsta n n yl)eth en yl)p er ylen e (1c). First
ol all, 2c was formed by a procedure analogous with that for
2a with 3c (0.75 g, 1.16 mmol) and tin tetrachloride (1 mL,
1.16 M in CH2Cl2) in CH2Cl2 (30 mL). After evaporation of the
solvent, washing with n-pentane, and drying under vacuum,
a yellow greenish powder of 2c was isolated. Yield: 0.56 g
1
C
24H19Cl3Sn): C, 55.2 (55.7); H, 4.1 (4.1); Cl, 18.9 (20.0).
(96%). H NMR (300 MHz, DMSO, 293 K): δ 7.61 (d, 7.9, 1H,
3-(4-(Tr ih ex-1-yn ylsta n n yl)bu tyl)p er ylen e (1a ). In a
H6), 7.57 (d, 8.5, 1H, H12), 7.54 (d, 8.5, 1H, H7), 7.53 (d, 8.2,
Schlenk tube under a nitrogen atmosphere cooled to -78 °C,
8.3 mL (20.8 mmol) of n-butyllithium (2.5 M in hexanes) was
added dropwise to a solution of hex-1-yne (1.9 g, 23.1 mmol)
in anhydrous THF (6 mL) at 0 °C. After it was stirred at room
temperature for 30 min, the reaction mixture was cooled to
-78 °C and a solution of 2a (3.0 g, 5.6 mmol) in anhydrous
THF (50 mL) was slowly added. After it was returned to room
temperature, the mixture was stirred for a further 12 h. The
solvent was then removed under reduced pressure, the result-
ing solids were extracted into CH2Cl2, and the solution
obtained was filtered twice over anhydrous MgSO4. Evapora-
tion of the solvent and drying under vacuum at 50 °C gave an
1H, H1), 7.13 (d, 8.5, 1H, H4), 6.98 (d, 7.9, 1H, H9 10), 6.96
or
(d, 17.4, 1H, H18), 6.95 (d, 7.6, 1H, H9 10), 6.86 (dd, 8.5, 7.9,
or
1H, H5), 6.85 (dd, 8.5, 7.9, 1H, H8 11), 6.76 (dd, 8.5, 7.6, 1H,
or
H8 11), 6.71 (d, 8.2, 1H, H2), 6.11 (d, 17.4, 1H, H13). This
or
compound (0.5 g, 1 mmol), which is light and air sensitive,
was immediately reacted with 3.6 equiv of hex-1-ynyllithium
prepared from n-butyllithium 2.5 M in hexanes (1.46 mL, 3.6
mmol) and hex-1-yne (0.34 g, 4.1 mmol) in anhydrous THF
(10 mL). After the mixture was stirred overnight at room
temperature, a workup analogous with that for 1a ,b gave
crude 1c as an orange waxy solid. Final purification was
achieved by washing with n-pentane. Yield: 0.2 g (30%). 1H