H
P. Niermeier et al.
Paper
Synthesis
10-Allyl-1,8-diethynylanthracene (12)
1H NMR (500 MHz, CDCl3): δ = 9.29 (s, 1 H, H9a), 7.66 (d, 3JH,H = 6.9 Hz,
3
3
2 H, H2b/H7b), 7.55 (d, JH,H = 7.4 Hz, 2 H, H4a/H5a), 7.34 (dd, JH,H
=
Synthesis according to the general procedure for deprotection of the
trimethsilyl protecting groups using 10-allyl-1,8-bis[(trimethylsi-
lyl)ethynyl]anthracene (9; 1.00 g, 2.44 mmol) and K2CO3 (1.77 g, 12.8
mmol), stirring at r.t. for 3 d. Column chromatography (n-pentane, ∅
= 6 cm, l = 12 cm, Rf = 0.2) afforded 12 as a yellow solid; yield: 496 mg
(76%).
4
3
7.8 Hz, JH,H = 1.1 Hz, 2 H, H2a/H7a), 7.08 (t, JH,H = 7.7 Hz, 2 H,
H3a/H6a), 7.00 (dd, 3JH,H = 8.8 Hz, 3JH,H = 6.9 Hz, 2 H, H3b/H6b), 6.79 (d,
3JH,H = 8.8 Hz, 2 H, H4b/H5b), 6.51 (s, 1 H, H9b), 0.37 {s, 18 H,
[Si(CH3)3]2}, 0.35 {s, 18 H, [Si(CH3)3]2}, –0.43 [s, 9 H, Si(CH3)3], –0.45 [s,
9 H, Si(CH3)3].
13C{1H} NMR (125 MHz, CDCl3): δ = 158.8, 148.7, 145.4, 144.9, 136.0,
132.2 (C2b/C7b), 130.8, 130.4 (C2a/C7a), 128.1 (C4b/C5b), 126.3,
124.8 (C3a/C6a), 124.5 (C3b/C6b), 123.9 (C9a), 123.0 (C4a/C5a), 121.3,
118.3, 104.1, 103.5, 100.2, 99.5, 98.0, 96.7, 59.9 (C10b), 50.1 (C9b), 0.6
{[Si(CH3)3]2}, 0.5 {[Si(CH3)3]2}, –0.6 [Si(CH3)3], –1.9 [Si(CH3)3].
1H NMR (500 MHz, CDCl3): δ = 9.50 (s, 1 H, H9), 8.25 (d, 3JH,H = 9.0 Hz,
2 H, H4/H5), 7.79 (d, 3JH,H = 6.9 Hz, 2 H, H2/H7), 7.48 (dd, 3JH,H = 9.0 Hz,
3
3
3JH,H = 6.9 Hz, 2 H, H3/H6), 6.18 (ddt, JH,H = 17.3 Hz, JH,H = 10.5 Hz,
3
3JH,H = 5.5 Hz, 1 H, CH2CH=CH2), 5.07 (d, JH,H = 10.2 Hz, 1 H,
CH2CH=CHcis), 4.87 (d, 3JH,H = 17.3 Hz, 1 H, CH2CH=CHtrans), 4.36 (d, 3JH,H
= 5.5 Hz, 2 H, CH2CH=CH2), 3.61 (s, 2 H, 2 × C≡CH).
29Si{1H} NMR (99 MHz, CDCl3): δ = –5.6 [Si(CH3)3], –17.6 {[Si(CH3)3]2},
13C{1H} NMR (125 MHz, CDCl3): δ = 136.3 (CH2CH=CH2), 133.0, 131.6,
131.3 (C2/C7), 129.9, 126.1 (C4/C5), 125.3 (C3/C6), 123.6 (C9), 121.3,
116.6 (CH2CH=CH2), 82.8 (C≡CH), 82.0 (C≡CH), 32.2 (CH2CH=CH2).
–17.7 {[Si(CH3)3]2}, –18.2 [Si(CH3)3].
anti-Photodimer of 1,8-Bis[(trimethylsilyl)ethynyl]-10-methylan-
thracene (72-anti
)
MS (EI, 70 eV): m/z = 266.0 [M]+, 239.0 [M – C2H3]+.
Synthesis according to the general procedure for photodimerisation
reactions.
HRMS (EI): m/z calcd for C34H30Cl4Si2: 266.10900; found: 266.10859,
dev. [ppm]: 1.54, dev. [mmu]: 0.41.
1H NMR (500 MHz, CDCl3): δ = 7.24–7.26 (m, 4 H, H4/H5), 7.00 (dd,
4
3
3JH,H = 7.7 Hz, JH,H = 1.0 Hz, 4 H, H2/H7), 6.84 (t, JH,H = 7.7 Hz, 4 H,
1,8-Diethynyl-9-methylanthracene (16)
H3/H6), 5.24 (s, 2 H, H9), 2.47 (s, 6 H, CH3), 0.37 [s, 36 H, Si(CH3)3].
Synthesis according to the general procedure for deprotection of the
trimethsilyl protecting groups using 1,8-bis[(trimethylsilyl)ethynyl]-
9-methylanthracene (15; 200 mg, 0.52 mmol) and K2CO3 (218 mg,
1.58 mmol), stirring at r.t. for 1 h. Filtration over silica gel with CH2Cl2
afforded 16 as a yellow solid; yield: 109 mg (87%).
13C{1H} NMR (125 MHz, CDCl3): δ = 146.3, 144.5, 130.7 (C2/C7), 125.5
(C3/C6), 123.4 (C4/C5), 121.6, 105.7 (C≡C–Si), 98.1 (C≡C–Si), 57.2 (C9),
52.3 (C10), 25.3 (ArCH3), 0.5 [Si(CH3)3].
29Si{1H} NMR (99 MHz, CDCl3): δ = –18.0.
1H NMR (500 MHz, CDCl3): δ = 8.25 (s, 1 H, H10), 7.93 (d, 3JH,H = 8.4 Hz,
2 H, H4/H5), 7.85 (d, 3JH,H = 6.9 Hz, 2 H, H2/H7), 7.36 (dd, 3JH,H = 8.3 Hz,
3JH,H = 7.0 Hz, 2 H, H3/H6), 3.78 (s, 3 H, CH3), 3.60 (s, 2 H, 2 × C≡CH).
anti-Photodimer of 1,8-Bis[(trimethylsilyl)ethynyl]-10-hexylan-
thracene (82-anti
)
13C{1H} NMR (125 MHz, CDCl3): δ = 136.3 (C2/C7), 134.7, 132.0, 132.0,
130.7 (C4/C5), 127.1 (C10), 124,4 (C3/C6), 119.4, 86.4 (C≡CH), 84.0
(C≡CH), 24.6 (CH3).
Synthesis according to the general procedure for photodimerisation
reactions.
1H NMR (500 MHz, CDCl3): δ = 7.14 (d, 3JH,H = 8.0 Hz, 4 H, H4/H5), 6.99
(d, 3JH,H = 7.6 Hz, 4JH,H = 1.0 Hz, 4 H, H2/H7), 6.80 (t, 3JH,H = 7.7 Hz, 4 H,
H3/H6), 5.18 (s, 2 H, H9), 3.11–3.17 (m, 4 H, CH2(CH2)4CH3), 1.46–1.54
(m, 4 H, CH2), 1.21–1.31 [m, 12 H, 3 × CH2], 0.87 (t, 3JH,H = 6.9 Hz, 6 H,
2 × CH3), 0.37 [s, 36 H, Si(CH3)3].
MS (EI, 70 eV): m/z = 240.0 [M]+.
+
HRMS (MALDI-TOF): m/z calcd for
C
19H12
:
240.09335; found:
240.0928, dev. [ppm]: 2.29, dev. [mmu]: 0.55.
13C{1H} NMR (125 MHz, CDCl3): δ = 144.7, 143.4, 130.9 (C2/C7), 126.0
(C4/C5), 125.0 (C3/C6), 121.8, 105.9 (C≡C–Si), 97.9 (C≡C–Si), 58.2
(C10), 57.7 (C9), 37.2 [CH2(CH2)4CH3], 32.1 (CH2), 30.8 (CH2), 25.6
(CH2), 22.8 (CH2), 14.1 (CH3), 0.6 [Si(CH3)3].
Photodimerisation Reactions; General Procedure
In an NMR tube small amounts (3–5 mg) of the respective anthracene
derivative were dissolved in anhyd and degassed CDCl3 (0.5 mL). The
mixtures were irradiated with UV light (365 nm) until no more sig-
nals of the reactant could be observed in the 1H NMR spectrum.
29Si{1H} NMR (99 MHz, CDCl3): δ = –18.1.
anti-Photodimer of 10-Allyl-1,8-bis[(trimethylsilyl)ethynyl]an-
anti-Photodimer of 1,8-Bis[(trimethylsilyl)ethynyl]anthracene
thracene (92-anti
)
(12-anti
)
Synthesis according to the general procedure for photodimerisation
reactions.
Synthesis according to the general procedure for photodimerisation
reactions.
1H NMR (500 MHz, CDCl3): δ = 7.05 (d, 3JH,H = 7.3 Hz, 4 H, H4/H5), 6.97
(d, 3JH,H = 7.7 Hz, 4 H, H2/H7), 6.79 (t, 3JH,H = 7.6 Hz, 4 H, H3/H6), 5.54
(s, 2 H, H9), 4.54 (s, 2 H, H10), 0.38 [s, 36 H, Si(CH3)3].
13C{1H} NMR (125 MHz, CDCl3): δ = 144.2, 143.4, 130.3 (C2/C7), 126.4
(C4/C5), 125.8 (C3/C6), 121.8, 104.5 (C≡C–Si), 98.2 (C≡C–Si), 52.2
(C10), 48.8 (C9), 0.6 [Si(CH3)3].
1H NMR (500 MHz, CDCl3): δ = 7.18 (d, 3JH,H = 7.7 Hz, 4 H, H4/H5), 7.00
(d, 3JH,H = 7.7 Hz, 4 H, H2/H7), 6.80 (t, 3JH,H = 7.7 Hz, 4 H, H3/H6), 5.46
3
3
3
(ddt, JH,H = 17.2 Hz, JH,H = 10.5 Hz, JH,H = 5.2 Hz, 2 H, CH2CH=CH2),
5.27 (d, 3JH,H = 17.5 Hz, 2 H, CH2CH=CHtrans), 5.19 (s, 2 H, H9), 5.05 (dd,
3JH,H = 10.5 Hz, 2JH,H = 1.3 Hz, 2 H, CH2CH=CHcis), 4.14 (d, 3JH,H = 5.1 Hz, 4
H, CH2CH=CH2), 0.39 [s, 36 H, Si(CH3)3].
13C{1H} NMR (125 MHz, CDCl3): δ = 144.6, 143.4, 136.8 (CH2CH=CH2),
130.8 (C2/C7), 126.1 (C4/C5), 125.2 (C3/C6), 121.8, 116.5
(CH2CH=CH2), 105.8 (C≡C–Si), 98.3 (C≡C–Si), 57.1 (C9), 56.4 (C10),
39.6 (CH2CH=CH2), 0.6 [Si(CH3)3].
29Si{1H} NMR (99 MHz, CDCl3): δ = –17.8.
Non-Classical [4π+2π] Photodimer of 1,8,10-Tris[(trimethylsi-
lyl)ethynyl]anthracene (22a
)
29Si{1H} NMR (99 MHz, CDCl3): δ = –17.9.
Synthesis according to the general procedure for photodimerisation
reactions.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–J