Synthesis and structure of bis(2,5-Dioxopyrrolidin-1-yl)adipate

Article abstract of DOI:10.14233/ajchem.2014.18358

bis(2,5-Dioxopyrrolidin-1-yl)adipate was prepared from adipate. Its structure was determined by single crystal X-ray diffraction analysis. The crystals are monoclinic space group P2₁/c with a = 5.2972(3), b = 7.5196(5), c = 19.2660(13) ?, α = 90.00, β = 99.776(6), γ = 90.00°, V = 756.28(8) ?³, Z = 2, F(000) = 356.0, D_c = 1.494 g/cm³, μ = 1.070 mm^-1, the final R = 0.0511 and wR = 0.1135. A total of 2484 reflections were collected, of which 1342 were independent (R_int = 0.0255).

Full text of DOI:10.14233/ajchem.2014.18358

Asian Journal of Chemistry; Vol. 26, No. 24 (2014), 8569-8571
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.18358
Synthesis and Structure of bis(2,5-Dioxopyrrolidin-1-yl)adipate
1
1
2,*
JINGYU ZHANG , XUAN ZHAO and XUEHUI HOU
1
2
School of Pharmacy Henan University of Traditional Chinese Medicine, Zhengzhou 450008, P.R. China
Department of Quality Detection and Management, Henan University of Animal Husbandry and Economy, Zhengzhou 450011, P.R. China
*
Corresponding author: Tel/Fax: +86 371 86176305; E-mail: houxh2006@163.com
Received: 20 June 2014; Accepted: 15 September 2014; Published online: 1 December 2014;
AJC-16405
bis(2,5-Dioxopyrrolidin-1-yl)adipate was prepared from adipate. Its structure was determined by single crystal X-ray diffraction analysis.
The crystals are monoclinic space group P2 /c with a = 5.2972(3), b = 7.5196(5), c = 19.2660(13) Å, α = 90.00, β = 99.776(6), γ = 90.00°,
1
3
3
-1
V = 756.28(8) Å , Z = 2, F(000) = 356.0, D = 1.494 g/cm , µ = 1.070 mm , the final R = 0.0511 and wR = 0.1135. A total of 2484
c
reflections were collected, of which 1342 were independent (Rint = 0.0255).
Keywords: Adipate derivative, Synthesis, Crystal structure.
4
INTRODUCTION
with SHELXS-97 and refined by the full-matrix least squares
5
method on F data using SHELXL-97 . The empirical absor-
2
Adipate derivative and N-hydroxy succinimide derivatives
ption corrections were applied to all intensity data. H atom of
N-H was initially located in a difference Fourier map and were
refined with the restraint Uiso(H) = 1.2 Ueq(N). Other H atoms
were positioned geometrically and refined using a riding
model, with d(C-H) = 0.93-0.97 Å and Uiso(H) = 1.2 Ueq(C)
or 1.5 Ueq(C-methyl).
Synthesis of title compound: As shown in Scheme-I, to
a solution of N-hydroxy succinimide (0.05 mol) in tetrahy-
drofuran (80 mL) was added a solution of dicyclohexyl-
carbodiimide (DCC) (0.175 mol) in tetrahydrofuran (20 mL).
The mixture was heated to 55 °C under stirring and kept for
are important structural elements in the preparation of poly-
peptide or antisense oligonucleotides (ODNs) which have a
diverse range of clinical applications in the treatmentof a variety
1
2
3
of diseases such as viral infection , tumor , vessel restenosis ,
4
5
fulminant septic shock , asthma and allergies . In our earlier
paper, we have reported the application of N-hydroxy succini-
6
mide derivative on the synthesis of antisense oligonucleotides .
To improve the function of compounds with new and attractive
characteristics, structural modifications of linker have been
extensively investigated. As a periodical result, we report
a novel linker derivative for the preparation of modified
nanogold.
1
h. Then compound 1 was added to the mixture stirring for
another 2 h at room temperature. After the compound 1
disappeared by TLC detection, the mixture was filtered and
the filtrate was evaporated under diminished pressure. The
residue was dissolved with ethyl acetate (50 mL) and washed
with saturated sodium chloride, water, orderly. Then the organic
phase was dried over anhydrous MgSO
of the dry solution gave 2 as a white ceraceous solid (76 %
yield). HRMS: Calcd for C14 340.0907; found
EXPERIMENTAL
Determination of crystal structure: The crystal of title
compound with dimensions of 0.26 mm × 0.24 mm × 0.20
mm was mounted on Xcalibur Eos Gemini diffractometer with
4
for 8 h. Evaporation
a graphite-monochromated CuK
by using a phi and scan modes at 291.15(2) K in the range of
.32º ≤ 2θ ≤ 133.96º. The crystal belongs to monoclinic system
with space group P2 /c and crystal parameters of a = 5.2972(3),
b = 7.5196(5), c = 19.2660(13) Å, α = 90.00, β = 99.776(6), γ
α
radiation (λ = 1.54184 Å)
H
16
O
8
N
2
+
9
3
41.0990 [M + H] .
1
RESULTS AND DISCUSSION
3
=
90.00°, V = 756.28(8) Å , Z = 2, F(000) = 356.0, D
c
= 1.494
g/cm . The absorption coefficient µ = 1.070 mm . The final
= 0.0404 (> 2σ(I)) and wR = 0.1028. A total of 2484
reflections were collected, of which 1342 were independent
int = 0.0255). The structure was solved by direct methods
Slow evaporation of title compound in MeOH and EtOAc
1:1) afforded colourless crystals suitable for X-ray analysis.
Structure of the title compound: The structure of title
compound 2 has been confirmed by single crystal X-ray diff-
3
-1
(
R
1
2
(R
raction analysis. Crystallographic and refinement parameters

8
570 Zhang et al.
Asian J. Chem.
OH
N
TABLE-1
O
O
O
O
O
CRYSTAL DATA AND STRUCTRE
REFINEMENT OF TITLE COMPOUND
O
O
N
HO
N
O
OH
THF/DCC
O
O
Items
Values
C H N O
8
340.29
O
O
Empirical formula
Formula weight
Crystal system
1
4
16
2
1
2
Scheme-I: Route for the synthesis of compound 2
Monoclinic
Unit cell dimensions
are given in Table-1. The selected bond lengths and bond angles
are listed in Tables 2-4, respectively. The structure was solved
by direct methods. Anisotropic displacement parameters were
applied to all nonhydrogen atoms in full-matrix least-square
refinements based on F . The hydrogen atoms were set in
calculated positions with a common fixed isotropic thermal
parameter.
a/Å
b/Å
c/Å
5.2972(3)
7.5196(5)
19.2660(13)
Unit cell angles (°)
2
α/°
β/°
γ/°
90.00
99.776(6)
90.00
756.28(8)
2
3
The molecular structure and the packing view of the title
compound are shown in Figs. 1 and 2, respectively.
Volume/Å
Z
Temperature (K)
Space group
Calculated density (g/cm )
291.15
P2 /c
1
3
1.494
1.070
-1
µ(mm )
F(000)
365.0
3
Crystal size (mm )
θ Range for data collection (°)
Reflections collected
0.26 × 0.24 × 0.20
9.32 to 133.96
2484
2
Independent reflections
1342[Rint = 0.0255]
Final R indexes [I ≥ 2σ(I)]
R = 0.0404, wR = 0.1135
1 2
Fig. 1. Molecular structure of the title compound
TABLE-2
SELECTED BOND LENGTHS [Å] OF TITLE COMPOUND
Bonds lengths
O1-C1
X-Ray crystal
1.200(3)
Bonds lengths
N1-C1
X-Ray crystal
1.375(3)
O2-C4
O3-N1
1.191(3)
1.387(2)
N1-C4
C7-C7’
1.390(3)
1.524(3)
1
O3-C5
-X, -Y, -Z
1.411(2)
O4-C5
1.182(2)
1
1
The title compound crystallizes in the monoclinic space
group P2 /c. The unit cell contains two molecules of title com-
1
pound.As can be seen in Fig. 1, the molecular structure consists
of two five-member ring (N1, C1, C2, C3, C4 and N1A, C1A,
C2A, C3A, C4A) which are fairly planar with plane equation
-
0
3.4768 (0.0044) × -5.6710 (0.0054) y + 1.7512 (0.0199) z =
.4919 (0.0084). The distance of the two planes is 4.460 Å
and the centre distance of the five-members rings is 12.983 Å.
There is no any classic intermolecular or intramolecular
7
,8
hydrogen bonds in the structure cell , which maybe the
primary reason that the compound possesses a lower melt point
(
56 °C).
Fig. 2. Crystal packing for the title compound
TABLE-3
SELECTED BOND ANGLES [º] AND TORSIONAL ANGLES [º] OF TITLE COMPOUND
Bonds angles
N1-O3-C5
O3-N1-C4
C1-N1-O3
C1-N1-C4
O1-C1-N1
O1-C1- C2
N1-C1-C2
C1-C2-C3
X-ray crystal
112.52(14)
120.25(16)
122.89(17)
116.85(17)
125.1(2)
129.71(19)
105.24(18)
106.41(16)
Bonds angles
O2--C4-N1
O2-C4-C3
N1-C4-C3
O3-C5-C6
O4-C5-O3
O4-C5- C6
C5-C6-C7
X-ray crystal
124.08(19)
130.5(2)
105.37(17)
107.80(15)
121.64(16)
130.56(19)
113.29(16)
111.8(2)
1
C6-C7-C7
1
1
-X, -Y, -Z

Vol. 26, No. 24 (2014)
Synthesis and Structure of bis(2,5-Dioxopyrrolidin-1-yl)adipate 8571
TABLE-4
SELECTED BOND TORSIONAL ANGLES [º] OF TITLE COMPOUND
Bonds angles
O1-C1-C2-C3
O3-N1-C1-O1
O3-N1-C4-C3
O4-C5-C6-C7
N1-O3-C5-C6
C1-N1-C4-O2
C1-C2-C3-C4
C2-C3-C4-N1
C4-N1-C1-C2
C5-O3-N1-C4
X-ray crystal
-178.1(2)
1.3(3)
175.45(17)
1.5(3)
-169.59(16)
175.4(2)
-5.5(2)
Bonds angles
O3-N1-C1-C2
O3-N1-C4-O2
O3-C5-C6-C7
N1-O3-C5-O4
N1-C1-C2-C3
C1-N1-C4-C3
C2-C3-C4-O2
C4-N1-C1-O1
C5-O3-N1-C1
X-ray crystal
-179.05(17)
-3.3(3)
-178.92(17)
10.1(3)
2.3(2)
-5.8(2)
-174.7(2)
-177.4(2)
-93.8(2)
6.6(2)
2.2(2)
84.8(2)
1
C5-C6-C7-C7
-173.1(2)
2
3
.
.
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Supplementary material: CCDC 1009056 contains the
supplementary crystallographic data for this paper. These data
can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html or from the Cambridge CrystallographicData
Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK
4
.
(Fax: +44-1223-336033; email: deposit@ ccdc.cam.ac.uk or
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ACKNOWLEDGEMENTS
5
5, 94 (2014).
The authors are grateful for the financial support from
the Education Department of Henan Province Science and
Technology Research Projects (No.14A150052) and the Scien-
tific Research Plan of Zhenzhou (No. 121PPTGG509-2).
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