1888 J. Phys. Chem. A, Vol. 108, No. 11, 2004
Nishikawa et al.
3H), 2.17-2.26 (m, 1H), 2.73-2.82 (m, 4H), 3.25 (s, 4H), 3.96
(t, J ) 10.4 Hz, 2H), 4.23 (dd, J ) 4.8, 11.2 Hz, 2H), 5.61 (s,
1H), 7.14 (d, J ) 6.4 Hz, 1H), 7.20-7.27 (m, 2H), 7.58 (d, J
) 6.8 Hz, 1H). 13C NMR (CDCl3): δ 15.38, 25.85, 30.28, 31.28,
31.48, 35.85, 67.58, 100.07, 105.59, 114.04, 115.57, 119.47,
126.50, 126.68, 128.89, 129.58, 134.50, 136.46, 138.76.
MS(EI): m/z 534(M+). Anal. Calcd for C22H24O2S7: C, 48.49;
H, 4.44. Found: C, 48.17; H, 4.56.
MS(EI): m/z 485(M+). Anal. Calcd for C19H18OS7: C, 46.88;
H, 3.73. Found: C, 46.85; H, 3.84.
4.4. General Procedure for Synthesis of Hydrazone (5a-
c). The synthesis of 5a is representative. A mixture of 4a (250
mg, 0.59 mmol) and p-toluenesulfonyl hydrazide (172 mg, 0.92
mmol) in THF (30 mL) was refluxed under nitrogen for 2 h.
After concentration under reduced pressure, the residue was
subjected to column chromatography on silica gel, using CH2Cl2
as an eluent, to afford 303 mg (0.47 mmol) of 5a (80% yield).
4.2.2. 5′-{3-[3-(1,3-Dioxan-2-yl)phenyl]propylthio}-4′-meth-
1
yl-4,5-ethylenedithiotetrathiafulValene (3b). Red oil. H NMR
4.4.1. 2-[3-(4′-Methyl-4,5-ethylenedithiotetrathiafulValen-5′-
ylthio)propyl]benzaldehyde p-toluenesulfonylhydrazone (5a).
(CDCl3): δ 1.43 (d, J ) 13.6 Hz, 1H), 1.90 (m, 2H), 2.13 (s,
3H), 2.16-2.24 (m, 1H), 2.69 (m, 4H), 3.24 (s, 4H), 3.98 (t,
2H), 4.25 (dd, J ) 4.0, 11.2 Hz, 2H), 5.48 (s, 1H), 7.13 (d, J
) 7.6 Hz, 1H), 7.25-7.31 (m, 3H). 13C NMR (CDCl3): δ 15.35,
25.78, 30.24, 30.98, 34.29, 35.39, 67.40, 101.60, 105.32, 114.03,
115.46, 119.34, 123.85, 125.96, 128.39, 128.94, 134.78, 138.89,
141.03. MS(EI): m/z 543(M+). Anal. Calcd for C22H24O2S7:
C, 48.49; H, 4.44. Found: C, 47.45; H, 4.32.
1
Orange solid; mp, 97-98 °C. H NMR (CDCl3): δ 1.78 (t, J
) 7.2 Hz, 1H), 2.10 (s, 3H), 2.40 (s, 3H), 2.64 (t, J ) 7.0 Hz,
2H), 2.80 (t, J ) 7.6 Hz, 2H), 3.27 (s, 4H), 7.12 (d, J ) 8.0
Hz, 1H), 7.19 (t, J ) 7.4 Hz, 1H), 7.27 (d, J ) 7.2 Hz, 1H),
7.31 (d, J ) 7.6 Hz, 2H), 7.63 (d, J ) 7.6 Hz, 1H), 7.87 (d, J
) 8.4 Hz, 2H), 8.02 (s, 1H), 8.57 (s, 1H). 13C NMR (CDCl3):
δ 15.40, 21.67, 30.29, 30.98, 31.64, 35.39, 114.09, 119.23,
126.65, 128.05, 128.41, 129.81, 130.30, 130.86, 134.84, 135.43,
140.29, 144.39, 146.71. Anal. Calcd for C26H26N2O2S8: C,
47.67; H, 4.00; N, 4.28. Found: C, 47.17; H, 4.43; N, 3.91.
4.2.3. 5′-{3-[4-(1,3-Dioxan-2-yl)phenyl]propylthio}-4′-meth-
1
yl-4,5-ethylenedithiotetrathiafulValene (3c). Red oil. H NMR
(CDCl3): δ 1.43 (d, J ) 13.7 Hz, 1H), 1.92-1.96 (m, 2H),
2.13 (s, 3H), 2.19-2.24 (m, 1H), 2.70 (t, J ) 6.0 Hz, 2H),
2.80 (t, J ) 7.4 Hz, 2H), 3.26 (s, 4H), 3.97 (t, J ) 12.3 Hz,
2H), 4.24 (dd, J ) 4.8, 10.4 Hz, 2H), 5.28 (s, 1H), 7.33 (d, J
) 8.0 Hz, 2H), 7.80 (d, J ) 8.0 Hz, 2H). 13C NMR (CDCl3):
δ 15.35, 25.77, 30.21, 31.02, 34.06, 35.18, 67.35, 101.59,
113.91, 119.28, 126.12, 128.20, 129.12, 130.02, 135.01, 136.64,
141.62. MS(EI): m/z 543(M+). Anal. Calcd for C22H24O2S7:
C, 48.49; H, 4.44. Found: C, 48.14; H, 4.41.
4.4.2. 3-[3-(4′-Methyl-4,5-ethylenedithiotetrathiafulValen-5′-
ylthio)propyl]benzaldehyde p-toluenesulfonylhydrazone (5b).
Orange solid; mp, 77-78 °C. 1H NMR (CDCl3): δ 1.84-1.89
(m, 2H), 2.11 (s, 3H), 2.38 (s, 3H), 2.63-2.69 (m, 4H), 3.27
(s, 4H), 7.15 (d, J ) 7.6 Hz, 1H), 7.24 (t, J ) 7.6 Hz, 1H),
7.29 (d, J ) 7.6 Hz, 2H), 7.35 (s, 1H), 7.40 (d, J ) 7.6 Hz,
1H), 7.73 (s, 1H), 7.87 (d, J ) 8.4 Hz, 2H), 8.53 (s, 1H). 13C
NMR (CDCl3): δ 15.38, 21.62, 30.24, 30.92, 33.98, 35.10,
105.44, 114.01, 115.26, 125.15, 127.49, 127.95, 128.80, 129.66,
130.68, 133.36, 134.94, 135.37, 141.54, 144.24, 147.98. Anal.
Calcd for C26H26N2O2S8: C, 47.67; H, 4.00; N, 4.28. Found:
C, 46.35; H, 4.00; N, 4.13.
4.3. General Procedure for Synthesis of Aldehydes (4a-
c). The synthesis of 4a is representative. A mixture of 3a (360
mg, 0.66 mmol) and pyridinium p-toluenesulfonic acid (5 mg,
0.02 mmol) in acetone (25 mL) and water (5 mL) was refluxed
under nitrogen overnight, and acetone was removed under
reduced pressure. The residue was extracted with CH2Cl2 and
washed with water. Purification by column chromatography on
silica gel, using a CH2Cl2-n-hexane (2:1) mixture as an eluent,
was performed to afford 250 mg (0.59 mmol) of 4a (89% yield).
4.3.1. 5′-[3-(2-Formylphenyl)propylthio]-4′-methyl-4,5-ethyl-
enedithiotetrathiafulValene (4a). Red oil. 1H NMR (CDCl3): δ
1.88-1.95 (m, 1H), 2.14 (s, 3H), 2.75 (t, J ) 7.0 Hz, 2H),
3.14 (t, J ) 7.4 Hz, 2H), 3.28 (s, 4H), 7.28 (d, J ) 7.2 Hz,
1H), 7.40 (t, J ) 7.6 Hz, 1H), 7.52 (t, J ) 7.2 Hz, 1H), 7.81 (d,
J ) 6.8 Hz, 1H), 10.21 (s, 1H). 13C NMR (CDCl3): δ 15.34,
30.23, 31.33, 35.49, 105.59, 114.05, 119.19, 126.83, 131.12,
133.11, 133.77, 134.78, 143.65, 192.48. MS(EI): m/z 485(M+).
Anal. Calcd for C19H18OS7: C, 46.88; H, 3.73. Found: C, 46.72;
H, 3.72.
4.3.2. 5′-[3-(3-Formylphenyl)propylthio]-4′-methyl-4,5-ethyl-
enedithiotetrathiafulValene (4b). Red oil. 1H NMR (CDCl3): δ
1.91-1.97 (m, 2H), 2.14 (s, 3H), 2.41 (t, J ) 7.0 Hz, 2H),
2.71 (t, J ) 7.6 Hz, 2H), 3.29 (s, 4H), 7.45-7.47 (m, 2H),
7.69-7.74 (m, 2H), 10.00 (s, 1H). 13C NMR (CDCl3): δ 15.40,
30.28, 30.90, 34.04, 35.20, 105.85, 114.04, 115.18, 119.11,
127.93, 129.36, 134.86, 135.02, 136.73, 142.15, 192.38.
MS(EI): m/z 485(M+). Anal. Calcd for C19H18OS7: C, 46.88;
H, 3.73. Found: C, 46.67; H, 3.77.
4.3.3. 5′-[3-(4-Formylphenyl)propylthio]-4′-methyl-4,5-ethyl-
enedithiotetrathiafulValene (4c). Red oil. 1H NMR (CDCl3): δ
1.88-1.98 (m, 2H), 2.13 (s, 3H), 2.70 (t, J ) 7.4 Hz, 2H),
2.80 (t, J ) 7.4 Hz, 2H), 3.28 (s, 4H), 7.33 (d, J ) 7.6 Hz,
2H), 7.80 (d, J ) 8.2 Hz, 2H), 9.97(s, 1H). 13C NMR (CDCl3):
δ 15.35, 30.23, 30.65, 34.50, 35.18, 105.93, 113.93, 114.03,
115.02, 119.02, 129.13, 130.04, 134.76, 135.01, 148.37, 191.82.
4.4.3. 4-[3-(4′-Methyl-4,5-ethylenedithiotetrathiafulValen-5′-
ylthio)propyl]benzaldehyde p-toluenesulfonylhydrazone (5c).
1
Red solid; mp, 165-166 °C. H NMR (CDCl3): δ 1.84-1.88
(m, 2H), 2.13 (s, 3H), 2.41 (s, 3H), 2.65-2.73 (m, 4H), 3.30
(s, 4H), 7.08 (d, J ) 8.1 Hz, 2H), 7.24 (d, J ) 8.6 Hz, 2H),
7.39 (d, J ) 8.1 Hz, 2H), 7.63 (s, 1H), 7.76 (d, J ) 8.3 Hz,
2H), 8.16 (s, 1H). 13C NMR (CDCl3): δ 15.37, 21.64, 30.31,
30.85, 34.22, 35.21, 100.82, 127.64, 127.98, 128.87, 129.73,
131.16, 134.91, 135.42, 141.33, 143.91, 144.27, 146.46, 147.94.
Anal. Calcd for C26H26N2O2S8: C, 47.67; H, 4.00; N, 4.28.
Found: C, 47.20; H, 4.02; N, 4.24.
4.5. General Procedure for Synthesis of C60-X-TTF. The
synthesis of C60-ortho-TTF is representative. A methanol
solution of NaOMe (28% × 102 mg, 0.53 mmol) was added to
a solution of 5a (303 mg, 0.47 mmol) in methanol (30 mL),
and the mixture was refluxed for 10 min under nitrogen. A
toluene (distilled from CaH2, 20 mL) solution of C60 (162 mg,
0.23 mmol) was successively added to the refluxing mixture,
and the resulting mixture was refluxed for 8 h. After water was
added, the mixture was extracted with toluene and washed with
water. The extracts were dried over MgSO4, concentrated under
reduced pressure, and purified by column chromatography on
silica gel, using carbon disulfide as an eluent, to afford 4.8 mg
(0.04 mmol) of C60-ortho-TTF in 8.4% yield (27% from reacted
C60).
4.5.1. 3′-{2-[3-(4′-Methyl-4,5-ethylenedithiotetrathiafulValen-
5′-ylthio)propyl]phenyl}-3′H-cyclopropa[1,9](C60-Ih)[5,6]-
fullerene (C60-ortho-TTF). Dark brown solid; mp, 220-222
°C dec. 1H NMR (CDCl3:CS2 ) 1:4): δ 1.91 (m, 2H), 2.08 (s,
3H), 2.65 (t, J ) 7.8 Hz, 2H), 2.82 (t, J ) 7.6 Hz, 2H), 3.26 (s,
4H), 4.01 (s, 1H), 7.32-7.34 (m, 1H), 7.38-7.40 (m, 2H),