1524 Bull. Chem. Soc. Jpn. Vol. 81, No. 11 (2008)
o-Hydroxybenzophenone Chromophore on SiO2
(0.06 g, 0.5 mmol) was stirred for 12 h at ambient temperature.
The reaction was monitored by TLC. The urea derived from
DCC was removed by filtration and the solution was concentrated.
The mixture was washed with acetic acid and then dried over
MgSO4. After evaporation, the crude product was purified by sili-
ca gel column chromatography using MeOH–CHCl3 (1:100) as
eluents and repeated recrystallization from EtOH–hexane (1:10)
to produce 2 as a white solid.
128.3, 129.6, 132.5, 132.9, 138.4, 150.9, 162.4, 169.2, 172.0,
194.2; IR (neat) 3298, 2964, 2935, 2875, 1770, 1651, 1612,
1566, 1549, 1200, 1163, 1109, 702, 638 cmꢁ1
.
General Procedure for the Preparation of 1a and 1b. SiO2–
NH2 (average diameter of beads: 8.3 mm, pore volume: 0.59
cm3 gꢁ1, xa: 1.50 mmol gꢁ1) was purchased from Fuji Sylisia
Chemical. SiO2–NH2 (1.0 g) and Im (0.10 g, 1.5 mmol) were add-
ed to a 2a and 2b (1.5 mmol) dichloromethane solution (2.0 mL).
The reaction mixture was gently agitated for 3 d at ambient tem-
perature. Then 1a and 1b was separated by filtration and washed
thoroughly with CHCl3 and MeOH.
The Degradation of 1 and 7. 1 and 7 were set in a thin layer
between two Pyrex glass plates. The photodegradation test was
performed in solid state >280 nm with irradiation from a high-
pressure mercury lamp under aerated conditions. Thermal degra-
dation of 1 and 7 were performed in an oven set at a given temper-
ature under aerated conditions.
Succinimidyl
4-(4-Benzoyl-3-hydroxyphenoxy)butanoate
1
(2a): Yield 86%. Mp 124–127 ꢃC. H NMR: ꢁ 2.26 (q, J ¼ 6:6
Hz, 2H), 2.85 (s, 4H), 2.86 (t, J ¼ 7:2 Hz, 2H), 4.14 (t, J ¼ 6:0
Hz, 2H), 6.43 (dd, Jortho ¼ 9:0 Hz, Jmeta ¼ 2:5 Hz, 1H), 6.52 (d,
Jmeta ¼ 2:4 Hz, 1H), 7.51 (d, Jortho ¼ 9:0 Hz, 1H), 7.46–7.53 (m,
2H), 7.54–7.59 (m, 1H), 7.61–7.66 (m, 2H), 12.65 (s, 1H);
13C NMR: ꢁ 24.3, 25.8, 27.8, 66.5, 101.9, 107.8, 113.5, 128.5,
129.0, 131.6, 135.5, 138.4, 165.3, 166.4, 168.3, 169.2, 200.2; IR
(KBr) 3059, 2947, 1819, 1786, 1743, 1639, 1373, 1350, 1265,
1217, 1117, 1076, 1043, 700, 650, 629 cmꢁ1; MALDI-TOFMS
Found: 398.3. Calcd for C21H18NO7: 397.1 ½M ꢁ Hþꢄ.
Supporting Information
Succinimidyl
11-(4-Benzoyl-3-hydroxyphenoxy)undec-
The following data are included: the fluorescence spectra of 7b
treated by 8, the UV spectra in the thermal and photochemical
degradations of 1b and 7b, and IR spectra in a range of 1800–
1500 cmꢁ1 for the thermal treatment of 1a and 1b at a given tem-
perature. This material is available free of charge on the web at
anoate (2b): Yield 66%. Mp 72–76 ꢃC. 1H NMR: ꢁ 1.32–1.50
(m, 12H), 1.73–1.79 (m, 4H), 2.60 (t, J ¼ 7:6 Hz, 2H), 2.83 (s,
4H), 4.02 (t, J ¼ 6:8 Hz, 2H), 6.40 (dd, Jortho ¼ 9:0 Hz, Jmeta
¼
2:5 Hz, 1H), 6.51 (d, Jmeta ¼ 2:4 Hz, 1H), 7.48–7.51 (m, 3H),
7.54–7.58 (m, 1H), 7.62–7.64 (m, 2H), 12.69 (s, 1H); 13C NMR:
ꢁ 24.3, 25.8, 27.8, 66.5, 101.9, 107.8, 113.5, 128.5, 129.0,
131.6, 135.5, 138.4, 165.3, 166.4, 168.3, 169.2, 200.2; IR (KBr)
2922, 2852, 1809, 1784, 1736, 1630, 1599, 1576, 1377, 1350,
1265, 1204, 1122, 1070, 810, 700, 629 cmꢁ1; MALDI-TOFMS
Found: 495.3. Calcd for C28H33NO7: 495.3 [Mþ].
References
1
W. B. Hardy, Commercial Aspects of Polymer Photostabi-
lization in Developments in Polymer Photochemistry 3, ed. by
N. S. Allen, Applied Science Publishers, New York, 1982,
Chap. 8, p. 287.
Preparation of N-Propyl-4-(4-benzoyl-3-hydroxyphenoxy)-
butanamide Derivatives 4a and 6a. 2a (0.20 g, 0.50 mmol)
was dissolved in dichloromethane (30 mL). Then propylamine
(0.03 g, 0.50 mmol) and Im (0.03 g, 0.50 mmol) were added. The
reaction mixture was stirred for 10 min at ambient temperature.
The reaction was monitored by TLC. After evaporation, the reac-
tion mixture was purified by silica gel column chromatography us-
ing MeOH–CHCl3 (1:20) as eluents and recrystallization from
EtOH–hexane (1:10) to give 4a as white solid (0.14 g, 0.45 mmol).
The acetylation was performed by the reaction of 4a (0.27 mmol)
with Ac2O (1 mL) in CHCl3–pyridine (2:1; 1.5 mL) at 80 ꢃC for
6 h to give 6a.
3
4
5
M. Hagiri, N. Ichinose, J. Kinugasa, T. Iwasa, T.
6
N-Propyl-4-(4-benzoyl-3-hydroxyphenoxy)butanamide (4a):
1
7
8
Y. Feng, D. Li, Y. Wang, D. G. Evans, X. Duan, Polym.
Yield 90%. Mp 93 ꢃC. H NMR: ꢁ 0.91 (t, J ¼ 7:4 Hz, 3H), 1.52
(sext, J ¼ 7:2 Hz, 2H), 2.16 (quint, J ¼ 6:6 Hz, 2H), 2.37 (t,
J ¼ 7:1 Hz, 2H), 3.23 (q, J ¼ 7:1 Hz, 2H), 4.08 (t, J ¼ 6:0 Hz,
2H), 5.45 (brs, 1H), 6.40 (dd, Jortho ¼ 9:0 Hz, Jmeta ¼ 2:5 Hz,
1H), 6.50 (d, J ¼ 2:5 Hz, 1H), 7.47–7.52 (m, 2H), 7.50 (d,
J ¼ 8:8 Hz, 2H), 7.54–7.59 (m, 1H), 7.62–7.64 (m, 2H), 12.64
(s, 1H); 13C NMR: ꢁ 13.3, 22.9, 24.9, 32.8, 41.3, 67.4, 101.8,
107.4, 113.2, 128.3, 128.8, 131.5, 135.3, 138.3, 165.5, 166.2,
171.8, 200.0; IR (KBr) 3337, 3083, 2967, 2931, 1650, 1632,
1603, 1576, 1544, 1474, 1445, 1421, 1382, 1350, 1265, 1232,
L. Perioli, V. Ambrogi, B. Bertini, M. Ricci, M. Nocchetti,
9
11 M. A. Rodrigues, D. B. Tada, M. J. Politi, S. Brochsztain,
1205, 1194, 1123, 701, 631, 539 cmꢁ1
.
N-Propyl-4-(4-benzoyl-3-acetoxyphenoxy)butanamide (6a):
1
Yield 75%. Oil. H NMR: ꢁ 0.91 (t, J ¼ 7:4 Hz, 3H), 1.52 (sext,
14 S. F. Santos, M. L. Santos, L. E. Almeida, N. B. Costa,
I. F. Gimenez, K. Araki, I. Mayer, F. M. Engelmann, H. E. Toma,
15 V. Latour, T. Pigot, P. Mocho, S. Blanc, S. Lacombe,
J ¼ 7:2 Hz, 2H), 1.97 (s, 3H), 2.16 (q, J ¼ 6:4 Hz, 2H), 2.40 (t,
J ¼ 7:0 Hz, 2H), 3.23 (q, J ¼ 6:8 Hz, 2H), 4.08 (t, J ¼ 5:9 Hz,
2H), 5.81 (brs, 1H), 6.69 (d, J ¼ 2:3 Hz, 1H), 6.81 (dd, Jortho
¼
8:6 Hz, Jmeta ¼ 2:3 Hz, 1H), 7.42–7.46 (m, 2H), 7.52 (d, J ¼ 8:6
Hz, 2H), 7.54–7.58 (m, 1H), 7.70–7.73 (m, 2H); 13C NMR: ꢁ
11.3, 20.5, 22.9, 25.0, 32.7, 41.3, 67.5, 109.5, 111.6, 123.7,
16 J. Matsumoto, T. Matsumoto, Y. Senda, T. Shiragami, M.