A. Martinez et al. / Journal of Organometallic Chemistry 690 (2005) 2163–2171
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2.2.3. 3,30-(3,6-Dioxaoctane-1,8-diyldioxy)bis(2-
hydroxy-5-tert- butylbenzaldehyde) (3)
(18H, s, t-Bu), 5.18 (4H, s, CH2), 7.15 (2H, d, J
2.1 Hz, ArH), 7.19 (2H, d, J 2.1 Hz, ArH), 7.39 (3H,
m, ArH), 7.57 (1H s, ArH), 9.89 (2H, s, CHO), 10.93
(2H, s, OH). dc (63 MHz, CDCl3) 31.16, 34.20, 71.54,
120.06, 120.43, 121.65, 126.80, 127.35, 128.88, 137.18,
142.72, 146.54, 150.26, 196.84. m/z (ES) 491.1
(M + H+), 513.3 (M + Na+), 529.3 (M + K+).
The compound 3 was synthesized by using the same
procedure as for 2, from sodium hydride (480 mg of a
60% suspension in mineral oil, 11.86 mmol) in 4 cm3
dry DMSO, 1 (1 g, 5.15 mmol) in 4 cm3 dry DMSO
and triethylene glycol ditosylate (1.18 g, 5.15 mmol).
The crude product was dissolved in 10 cm3 diethyl ether
and precipitated with hexane (100 cm3). The resulting
yellow oil was recrystallized in hot cyclohexane, afford-
ing 3 as white crystals suitable for X-ray analysis
(400 mg, 31%). Calc. for C28H38O8: C, 66.85; H, 7.56.
Found: C, 66.52; H, 7.14%. dH (250 MHz, CDCl3)
1.29 ppm (18H, s, t-Bu), 3.77 (4H, s, OCH2), 3.89 (4H,
m, OCH2), 4.29 (4H, m, OCH2), 7.17 (2H, d, J 2.2 Hz,
ArH), 7.24 (2H, d, J 2.2 Hz, ArH), 9.92 (2H, s, CHO),
10.69 (2H, s, OH). dc (63 MHz, CDCl3) 31.16, 34.25,
69.10, 69.28, 70.66, 119.19, 119.86, 120.90, 142.66,
146.82, 149.98, 196.03. m/z (DCI/NH3) 520
ðM þ NHþ4 ; 100Þ. Suitable crystals were obtained for
X-ray analysis.
2.2.6. MnIII–Salen complex 6
The compound 2 (400 mg, 0.87 mmol) was dissolved
in 120 cm3 EtOH under a nitrogen atmosphere. To the
resulting solution was added successively (1S,2S)-(+)-
1,2-diaminocyclohexane (100 mg, 0.87 mmol) and man-
ganese (II) diacetate tetrahydrate (214 mg, 0.87 mmol).
After stirring overnight, dioxygen was bubbled through
the solution for 4 h. The reaction mixture was concen-
trated to 20 cm3, treated with 20 cm3 brine and extracted
with 2 · 50 cm3 CH2Cl2. The organic layer was washed
with 100 cm3 H2O and dried over Na2SO4. After evapo-
ration of the solvent and drying under vacuum, 404 mg
(74%) of complex 6 was obtained as a dark brown
microcrystalline solid. Calc. for C32H42N2O5ClMn Æ 2-
H2O: C, 58.14; H, 7.01; N, 4.24; Cl, 5.36; Mn, 8.31.
Found: C, 57.93; H, 7.29; N, 4.39; Cl, 5.60; Mn,
8.14%. m/z (ES) 589.2 (M ꢀ Cl). mmax/cmꢀ1 1616
2.2.4. 1,3-Benzenedimethanol-di-p-tosylate (4)
In a solution of 15 cm3 H2O and 3 g NaOH
(75.2 mmol), 4 g (29 mmol) of 1,3-benzenedimethanol
were dissolved. Over a period of 20 min, tosyl chloride
(12.16 g, 63.9 mmol) in 25 cm3 THF was added dropwise
and the resulting solution stirred overnight. The reaction
mixture was extracted with 100 cm3 toluene, washed with
100 cm3 H2O, 100 cm3 of a saturated NaHCO3 aqueous
solution and dried over Na2SO4. The crude product was
dissolved in 10 cm3 CH2Cl2 and precipitated with hexane
(100 cm3). The white precipitate was filtered off and dried
under vacuum (4.5 g, 35%). Calc. for C22H22O6S2 Æ 0.5
H2O: C, 58.02; H, 5.27. Found: C, 58.41; H, 5.02%. dH
(250 MHz, CDCl3) 2.44 ppm (6H, s, CH3), 4.98 (4H, s,
CH2), 7.09 (1H, s, ArH), 7.18–7.28 (3H, m, ArH), 7.30
(4H, d, J 8.7 Hz, TsH), 7.77 (4H, d, J 8.4 Hz, TsH). m/z
(ES) 469 (M + Na+, 100).
(C@N).
k
max/nm (MeOH) 278 (e/dm3 molꢀ1 cmꢀ1
16110), 326 (13110), 414 (5910). a (589 nm, 20 ꢁC,
0.048 g dmꢀ3 in MeOH, 10 cm path) = +0.0242ꢁ.
2.2.7. MnIII–Salen complex 7
The complex 7 was synthesized as described above,
starting from 2 (320 mg, 0.70 mmol) in 100 cm3 EtOH,
(1R,2R)-(+)-1,2-diaminocyclohexane (75 mg, 0.70 mmol)
and Mn(OAc)2 Æ 4H2O (171 mg, 0.70 mmol). Yield:
360 mg, 82% as a dark brown microcrystalline solid.
Calc. for C32H42N2O5ClMn Æ 1H2O: C, 59.77; H, 6.90;
N, 4.36; Cl, 5.52; Mn, 8.55. Found: C, 60.06; H, 6.85;
N, 4.00; Cl, 5.40; Mn, 8.58%. m/z (ES) 589.3 (M ꢀ Cl),
1213.6 ðMnIIISalen2ClÞ. mmax/cmꢀ1 1616 (C@N). kmax
/
2
nm (MeOH) 278 (e/dm3 molꢀ1 cmꢀ1 16110), 322
(13570), 412 (5500). a (589 nm, 20 ꢁC, 0.044 g dmꢀ3 in
MeOH, 10 cm path) = ꢀ0.0218ꢁ.
2.2.5. 3,30-(1,3-Benzenediyldioxy)bis(2-hydroxy-5-tert-
butylbenzaldehyde) (5)
The compound 5 was synthesized by using the same
procedure as for 2, from sodium hydride (440 mg of a
60% suspension in mineral oil, 10.67 mmol) in 6 cm3
dry DMSO, 1 (900 mg, 4.64 mmol) in 6 cm3 dry DMSO
and 4 (1.04 g, 2.32 mmol). The reaction was monitored
by 1H NMR, showing that starting 2,3-dihydroxy-5-
tert-butylbenzaldehyde was still present. Two subse-
quent portions of 4 (100 mg, 2.2 mmol) were thus added
at t = 12 and 24 h. The crude product was purified by
column chromatography (silicagel, hexane/ethyl acetate
(90/10) as eluent) and recrystallization in hot cyclohex-
ane, affording 151 mg of a white solid (13%). Calc. for
C30H34O6 Æ 0.1H2O: C, 73.18; H, 6.89. Found: C,
72.97; H, 6.51%. dH (250 MHz, CDCl3) 1.24 ppm
2.2.8. MnIII–Salen complex 8
The complex 8 was obtained as described for complex
6 from 2 (320 mg, 0.70 mmol) in 100 cm3 EtOH,
(1S,2S)-(ꢀ)-1,2-diphenylethylenediamine
(148 mg,
0.70 mmol) and Mn(OAc)2 Æ 4H2O (171 mg, 0.70 mmol).
Yield: 450 mg, 89% as a dark brown microcrystalline so-
lid. Calc. for C40H44N2O5ClMn Æ 2H2O: C, 63.28; H,
6.37; N, 3.69; Cl, 4.68; Mn, 7.24. Found: C, 63.35; H,
6.26; N, 3.40; Cl, 4.78; Mn, 7.54%. m/z (ES) 687.3
(M - Cl). mmax/cmꢀ1 1616 (C@N). kmax/nm (MeOH)
276 (e/dm3 molꢀ1 cmꢀ1 32500), 330 (21000), 422
(8360). a (589 nm, 20 ꢁC, 0.049 g dmꢀ3 in MeOH,
10 cm path) = +0.0212ꢁ.