The crystallographic structure of 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one

Article abstract of DOI:10.1023/A:1009517326150

The crystallographic structure of 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one 1 is disclosed by x-ray analysis. It crystallized in the space group C2/c (#15) with a = 19.958(4), b = 10.486(3), c = 15.009(3) A, β = 137.553(6)°, V = 2120.0(9)A°³

Full text of DOI:10.1023/A:1009517326150

Journal of Chemical Crystallography, Vol. 29, No. 12, 1999
Note
The crystallographic structure of 4-hydroxy-3-methylene-4-
(
p-nitrophenyl)butan-2-one
(
1)
Min Shi * and Jian-Kang Jiang
Received February 7, 2000
The crystallographic structure of 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one 1 is
disclosed by x-ray analysis. It crystallized in the space group C2/c (#15) with a ϭ 19.958(4),
˚
˚
3
3
b ϭ 10.486(3), c ϭ 15.009(3) A, ͱ ϭ 137.553(6)Њ, V ϭ 2120.0(9)A, Dcalc ϭ 1.386 g/cm , and
Z ϭ 8.
KEY WORDS: Baylis–Hillman reaction; 4-hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one.
Introduction
successfully employed in a plethora of stereoselective
processes.1 However, the crystal structures of the
–3
The Baylis–Hillman reaction continues to at-
products derived from Baylis–Hillman reaction have
never been disclosed before. This time, we success-
fully obtained a single crystal of 4-hydroxy-3-methyl-
ene-4-(p-nitrophenyl)butan-2-one 1 from the reac-
tion of p-nitrobenzaldehyde with methyl vinyl ketone
in the presence of titanium(IV) chloride and dimeth-
ylsulfide (Scheme 2). Herein, we wish to report the
x-ray crystallographic structure of this interesting
compound 1.
tract organic chemists as it constructs a novel car-
bonUcarbon bond between the Ͱ-position of acti-
vated alkenes and carbon electrophiles, leading to
the formation of a synthetically attractive and useful
class of molecules with chemospecific functional
1
–10
groups (Scheme 1).
The Baylis–Hillman adducts
derived from activated alkenes such as acrylate es-
ters, acrylonitrile, and phenyl vinyl sulfone have been
dehyde (151 mg, 1 mmol) and methyl vinyl ketone
Experimental
(
210 mg, 249 ȐL, 3 mmol) was added titanium(IV)
chloride (264 mg, 153 ȐL, 1.4 mmol) and dimethylsul-
fide (12.4 mg, 14.7 ȐL, 0.2 mmol) at Ϫ70ЊC. The
reaction mixture was stirred at Ϫ70ЊC for 16 h. The
reaction was quenched with 20 mL saturated
Compound 1 was prepared from the reaction of
p-nitrobenzaldehyde with methyl vinyl ketone in the
presence of titanium(IV) chloride and dimethylsul-
fide. To a dichloromethane solution of p-nitrobenzal-
NaHCO
romethane (10 mL ϫ 3). The organic layer was dried
over anhydrous MgSO . The solvent was removed
under reduced pressure, and the residue was purified
3
aqueous solution and extracted with dichlo-
(1)
Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin
Lu, Shanghai 200032 China.
4
1295
1
074-1542/99/1200-1295$16.00/0  1999 Plenum Publishing Corporation

1296
Shi and Jiang
Table 2. Atomic Coordinates and Biso/Beq
Atom
O(1)
O(2)
O(3)
O(4)
N
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
x
y
z
B
eq
0.3774(2)
0.3492(2)
0.2860(1)
0.5901(1)
0.3643(2)
0.3977(1)
0.3914(2)
0.3730(1)
0.3624(1)
0.3689(1)
0.3861(1)
0.3845(1)
0.4503(1)
0.5588(1)
0.4140(2)
0.6297(2)
0.7610(2)
0.6441(2)
0.1638(1)
0.2266(1)
0.6583(2)
0.4528(2)
0.5604(2)
0.5445(2)
0.4264(2)
0.3203(2)
0.3315(2)
0.2140(2)
0.1084(2)
0.1311(2)
Ϫ0.0008(2)
0.0368(2)
0.6248(3)
0.7018(2)
0.3406(1)
0.6368(2)
0.6446(2)
0.4782(2)
0.5246(2)
0.5964(2)
0.6247(2)
0.5771(2)
0.5029(2)
0.4418(2)
0.5413(2)
0.6428(2)
0.5361(2)
0.7514(2)
10.0(1)
6.72(6)
4.56(3)
4.74(4)
4.80(5)
3.46(4)
3.81(5)
3.32(4)
3.44(4)
3.42(4)
2.86(4)
3.15(4)
2.97(4)
3.28(4)
4.29(5)
4.71(5)
Fig. 1. Molecular structure of 1 (peripheral groups not shown).
by silica gel column chromatography to give com-
pound 1 as a colorless solid (199 mg, 90%). m.p.
Ϫ1
6
2
6
8
6–68ЊC; IR (KBr) ␯ 1720 cm (CuO); ͳ
H
(CDCl )
3
.36 (3H, s, Me), 3.26 (1H, br. s, OH), 5.68 (1H, s),
.05 (1H, s), 6.28 (1H, s), 7.56 (2H, d, J 8.6 Hz, Ar),
.19 (2H, d, J 8.6 Hz, Ar).
spectrum was recorded with a JMS D-300 instrument.
CHN microanalysis was carried out with a Perkin-
Elmer Model 240 analyzer.
The structure was solved by direct methods
(SHELXS86) and expanded using Fourier tech-
niques (DIRDIF92). The final cycle of full-matrix
least-square refinement was based on 2114 observed
reflections (I Ͼ 3.00␴(I)) and 209 variable parameters
and converged (largest parameter was 0.05 times its
esd) with unweighted and weighted agreement fac-
The melting point was obtained with a Yanagi-
moto micro melting point apparatus and is uncor-
1
rected. H NMR spectra were determined for a solu-
tion in CDCl with tetramethylsilane as an internal
3
standard on a JNM-GX 270 spectrometer. The mass
Table 1. Crystal Data and Structure Refinement
tors: R ϭ 0.047, R ϭ 0.061. The X-ray crystal struc-
w
Compound
CCDC deposit no.
Color/shape
Lattice type
Crystal system
Space group
11 11 4
C H O N
ture of 1 is shown in Fig. 1, and the X-ray data are
summarized in Table 1. Atomic coordinates are given
in Table 2.
CCDC-1003/5748
Yellow, prismatic
C-centered
Monoclinic
C2/c (#15)
Unit cell dimensions
(
7460 reflections in full ␪ range)
Results and discussions
˚
a ϭ 19.958(4) A
˚
b ϭ 10.486(3) A
Compound 1 could be readily separated by silica
gel column chromatography after reaction (eluent:
ethyl acetate/hexane ϭ 1/4). The structure of 1 was
˚
c ϭ 15.009(3) A
ͱ ϭ 137.553(6)Њ
˚
3
Volume, A
Z
Density (calculated), g/cm
F
Ȑ(MoKͰ)
Diffractometer/scan
Radiation, graphite monochromator MoKͰ (␭ ϭ 0.71069 A)
Crystal to detector distance
Temperature
2120.0(9)
8
1
first characterized by H NMR spectral data. The final
3
1
1.386
928.00
1.07 cm
structure was determined by comparing the H NMR
spectral data with that of the authentic sample.
(000)
11
Ϫ1
We successfully got the single crystal of 1 by
recrystallization from hexane and dichloromethane
(10/1). The x-ray crystallographic structure of 1 is
shown in Fig. 1, and the x-ray data are summarized
in Table 1.
Rigaku AFC7R
235 mm
20.0ЊC
55.0Њ
0.03
11.92
2
␳
␪
max
-factor
The CUC bond lengths of the six-membered
ring are essentially equivalent (1.377–1.392 A), and
Reflection/parameter ratio
˚

4-Hydroxy-3-methylene-4-(p-nitrophenyl)butan-2-one
1297
2
.
.
Basavaiah, D.; Dharma Rao, P.; Suguna Hyma, R. Tetrahe-
dron 1996, 52, 8001.
Giganek, E. Organic Reactions; 1997, 51, 201; Paquette, L.A.,
Ed., John Wiley & Sons: New York.
the benzene ring is completely planar. The bond
˚
UC10 is 1.326 A, which represents a dou-
length of C
ble bond. Meanwhile, the bond length of the carbonyl
8
3
˚
4. Buchholz, R.; Hoffmann, H.M.R. Helv. Chim. Acta 1991,
group is 1.219 A (O
4
UC ). All the bond lengths and
9
74, 1213.
bond angles are normal.
5
6
.
.
Amri, H.; Villieras, J. Tetrahedron Lett. 1986, 27, 4307.
Hoffmann, H.M.R.; Eggert, U.; Poly, W. Angew. Chem. Int.
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Daude, N.; Eggert, U.; Hoffmann, H.M.R. J. Chem. Soc.
Chem. Commun. 1988, 206.
Acknowledgment
7.
8.
9.
Matsumoto, S.; Okubo, Y.; Mikami, K. J. Am. Chem. Soc.
We thank the National Natural Sciences Foun-
dation of China for financial support.
1
998, 120, 4015.
Aggarwal, V. K.; Mereu, A.; Tarver, G.J.; McCague, R. J.
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1
1
0. Barrett, A.G.M.; Cook, A.S.; Kamimura, A. J. Chem. Soc.
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