An Efficient Synthesis of 1,5-Diaryl-1,4-pentadien-3-one Oxime
Letters in Organic Chemistry, 2010, Vol. 7, No. 4
325
Table 3. Condensation of 1,5-Diaryl-1,4-pentadien-3-one with Hydroxylamine Hydrochloride in EtOH Under Refluxing
Entry
Ar1
Ar2
Time (h)
Yield (%)
Mp (oC) (lit.)
2a
2b
2c
2d
2e
2f
C6H5
p-CH3C6H4
o-CH3OC6H4
p-CH3OC6H4
p-ClC6H4
m-ClC6H4
o-ClC6H4
p-BrC6H4
C6H5
C6H5
3
4
3
5
5
4
3
5
4
4
92
90
91
75
92
93
90
93
84
75
140-142(139-140)[10]
148-150
p-CH3C6H4
o-CH3OC6H4
p-CH3OC6H4
p-ClC6H4
150-152
139-140
176-178
m-ClC6H4
o-ClC6H4
159-160
2g
2h
2i
147-149
p-BrC6H4
170-171
p-CH3C6H4
p-CH3OC6H4
112-114
2j
C6H5
100-102
was followed by TLC) as indicated in Table 3. After
completion of the reaction, the mixture was filtered. And the
solvent was evaporated under reduced pressure. The residue
was accomplished by column chromatography on silica
(200-300 mesh), eluted with petroleum ether or a mixture of
petroleum ether and ethyl acetate. The known compound 2a
was established by its melting point compared with that
reported in literature [10a]. The preparation of 2d was also
reported in the literature [10b], but no melting point was
reported. The rests are new compounds, 2d and these new
ꢀ 6.87 (d, J=16.2 Hz, 2H, 2ArCH=), 7.02(d, 2H, J=15.9 Hz,
2CHC=N), 7.00-7.42(m, 8H, ArH); m/z (ESI) C17H13Cl2NO
[M-H] + 317.
Compound 2g
1,5-bis(2-chlorophenyl)penta-1,4-dien-3-one oxime.
White solid, m.p. 147-149oC.1H NMR (400 MHz, CDCl3) ꢀ
6.89 (d, J=16.3Hz, 2H, 2ArCH=), 7.28(d, 2H, J=15.9 Hz,
2CHC=N), 7.26-7.68(m, 8H, ArH); m/z (ESI) C17H13Cl2NO
[M-H] + 317.
1
compounds were established by their H NMR spectra and
Compound 2h
mass spectra. The hydrogen of N-OH didn’t appear in the
spectrum of 1H NMR.
1,5-bis(4-bromophenyl)penta-1,4-dien-3-one oxime.
1
White solid, m.p. 170-171oC. HNMR(400 MHz, CDCl3) ꢀ
Compound 2b
6.85 (d, J=16.2 Hz, 2H, 2ArCH=), 7.02(d, 2H, J=17.2 Hz,
2CHC=N), 6.99-7.53(m, 8H, ArH); m/z (ESI) C17H13Br2NO
[M-H] + 406.
1,5-bis(4-methylphenyl)penta-1,4-dien-3-one oxime.
o
White solid, m.p. 148-150 C. 1H NMR (400 MHz, CDCl3)
ꢀ 2.38(s, 6H, 2CH3), 6.85 (d, J=16.2 Hz, 2H, 2ArCH=),
7.10(d, 2H, J=6.2 Hz, 2CHC=N), 7.07-7.46 (m, 8H, ArH);
m/z (ESI) calcd for C19H19NO [M+H]+ 278.
Compound 2i
1-(4-methylphenyl)-5-phenylpenta-1,4-dien-3-one
o
1
Compound 2c
oxime. White solid, m.p. 112-114 C. HNMR (400 MHz,
CDCl3) ꢀ 2.38(s, 3H, CH3), 6.89 (d, J=16.2 Hz, 2H,
2ArCH=), 7.02(d, 2H, J=15.9 Hz, 2CHC=N), 7.10-7.57(m,
9H, ArH); m/z (ESI) C18H17NO [M-H] + 262.
1,5-bis(2-methoxyphenyl)penta-1,4-dien-3-one oxime.
1
White solid, m.p. 150-152oC. H NMR (400 MHz, CDCl3)
ꢀ 3.87(s, 6H, 2OCH3), 6.90 (d, J=8.3Hz, 2H, 2ArCH=),
6.98(d, 2H, J=3.3 Hz, 2CHC=N), 7.26-7.56(m, 8H, ArH);
m/z (ESI) C19H19NO3 [M-H] + 308.
Compound 2j
1-(4-methoxyphenyl)-5-phenylpenta-1,4-dien-3-one
Compound 2d
o
1
oxime. White solid, m.p. 100-102 C. HNMR (400 MHz,
CDCl3) ꢀ 3.84(s, 3H, OCH3), 6.79 (d, J=16.2 Hz, 2H,
2ArCH=), 7.02(d, 2H, J=15.9 Hz, 2CHC=N), 7.10-7.57(m,
9H, ArH); m/z (ESI) C18H17NO2 [M-H] + 278.
1,5-bis(4-methoxyphenyl)penta-1,4-dien-3-one oxime.
1
White solid, m.p. 139-140oC. H NMR (400 MHz, CDCl3)
ꢀ 3.84(s, 6H, 2OCH3), 6.76 (d, J=15.9 Hz, 2H, 2ArCH=),
7.10(d, 2H, J=5.4 Hz, 2CHC=N), 6.90-7.47(m, 8H,ArH);
m/z (ESI) C19H19NO3 [M+H] + 310.
ACKNOWLEDEGEMENT
Compound 2e
The project was supported by Natural Science
Foundation of Hebei Province (B2006000969), China.
1,5-bis(4-chlorophenyl)penta-1,4-dien-3-one oxime.
1
White solid, m.p. 176-178oC. H NMR (400 MHz, CDCl3)
ꢀ 6.84 (d, J=16.1 Hz, 2H, 2ArCH=), 7.03(d, 2H, J=16.8 Hz,
2CHC=N), 7.01-7.49(m, 8H, ArH); m/z (ESI) C17H13Cl2NO
[M-H] + 317.
REFERENCES
[1]
[2]
[3]
Li, J. T.; Li, X. L.; Li,T. S. Synthesis of oximes under ultrasound
irradiation. Ultrason. Sonochem., 2006, 13, 200.
Donaruma, L. G.; Helst, W. Z. The beckmann rearrangement. Org.
React., 1960, 11, 1.
(a) Smitha, P. A. S.; Robertson, J. E. Some factors affecting the site
of alkylation of oxime salts. J. Am. Chem. Soc., 1962, 84, 1197. (b)
Compound 2f
1,5-bis(3-chlorophenyl)penta-1,4-dien-3-one oxime.
1
White solid, m.p. 159-160oC. H NMR (400 MHz, CDCl3)