3J(H,H) = 7.6 Hz, 4J(H,H) = 1.4 Hz, 1H; aryl), 7.13 (dt, 3J(H,H) =
7.6 Hz, 4J(H,H) = 1.4 Hz, 1H; aryl), 7.36 (dd, 3J(H,H) = 7.6 Hz,
4J(H,H) = 1.4 Hz, 1H; aryl), 12.37 ppm (s, 1H; NH).
(Asahi tech.) to pick out the 313 nm emission line of Hg gas. At
TLC lamp was used for 254 nm UV-light irradiation, and UV-light
was filtered through a solution filter (aqueous solution of NiSO4,
CoSO4 and KI/I2). The sample was dissolved in the degassed
solvent under argon atmosphere and sealed in a quartz NMR
tube or UV cell. The spectrum was measured before and after
irradiation. During irradiation and spectrum measurements, the
sample was always kept at the desired temperature.
Preparation of (E)-3-(2-pivaloylaminophenyl) acrylic acid (Z-1)
The crystal of [tetramethylammonium](Z)-3-(2-pivaloylamino-
phenyl) acrylate (186.7 mg, 0.476 mmol) was suspended in ethyl
acetate. The suspension was acidified by adding 2% aqueous
hydrochloride, then the organic layer turned to a clear solution.
The aqueous layer was extracted with ethyl acetate twice, and
the combined organic layer was dried over anhydrous magnesium
sulfate. The solvent was removed under reduced pressure to obtain
a colorless oil. The oil was reprecipitated from diethylether–
n-hexane to obtain a white powder. Yield 117.8 mg (81.8%).
Mp 125 ◦C; found: C, 66.93; H, 6.99; N, 5.58. Calc. for
C14H17NO3·(H2O)0.2: C, 67.02; H, 6.99; N, 5.55%); dH(270 MHz;
Acknowledgements
One of the authors (T. Matsuhira) expresses his special thanks to
the Global Education and Research Center for Bio-Environmental
Chemistry (GCOE) program of Osaka University.
References
3
DMSO-d6) 1.20 (s, 9H; tert-butyl), 5.98 (d, J(H,H) = 12.5 Hz,
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Crystallographic data collections and structure determinations of
E-1 and Z-2
Suitable single crystals of E-1 and Z-2 were mounted on a
fine nylon loop with nujol and immediately frozen at 200
1 K. All measurements were performed on a Rigaku RAXIS-
RAPID Imaging Plate diffractometer with graphite monochro-
˚
mated MoKa radiation (k = 0.71075 A). The structures were
solved by direct method (SIR 92)9 and the subsequent refinements
were performed using SHELXL-9710 and teXsan crystallographic
software package. All non-hydrogen atoms were refined anisotrop-
ically. The coordinates of OH and NH protons were refined
using fixed thermal factors, and the other protons were placed
in calculated positions. Crystal data for C14H17NO3 (E-1): 0.30 ×
3
¯
˚
0.20 × 0.10 mm , triclinic, P1 (#2), a = 5.334(4) A, b = 9.149(7)
◦
◦
◦
˚
˚
A, c = 13.95(1) A, a = 74.60(3) , b = 80.12(3) , c = 82.77(2) ,
V = 644(3) A , Z = 2, qcalcd = 1.275 g cm−3, l(MoKa) = 0.89 cm−1,
3
˚
Mw = 247.29. Total number of reflections measured 6238, unique
reflections 2885 (Rint = 0.031), Final R indices: R1 = 0.043, wR2 =
0.120 for all data. GOF (F2) = 0.86. Crystal data for C18H28N2O3
(Z-2): 0.30 × 0.20 × 0.20 mm3, hexagonal, P63 (#173), a =
3
˚
˚
˚
21.127(5) A, c = 7.522(2) A, V = 2907(4) A , Z = 6, qcalcd
=
1.098 g cm−3, l(MoKa) = 0.74 cm−1, Mw = 320.43. Total number
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of reflections measured 27 898, unique reflections 27 887 (Rint
=
0.039), Final R indices: R1 = 0.041, wR2 = 0.098 for all data.
GOF (F2) = 1.03. CCDC 603981 and CCDC 603982 contain the
supplementary crystallographic data for this paper.†
UV-Light irradiation technique for UV–vis and 1H NMR spectrum
measurement
A Xe/Hg lamp (MUV-202U, Moritex Co.) was used for 313 nm
UV-light irradiation. UV-Light was filtered through 6784-t01.uv1
6 T. Matsuhira, H. Yamamoto, A. Onoda, T. Okamura and N. Ueyama,
Org. Biomol. Chem., 2006, 4, 1338–1342.
1932 | Org. Biomol. Chem., 2008, 6, 1926–1933
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