Molecular and crystal structure of 2-(2-p-tolyloxyethoxy)ethylchloroacetate

Article abstract of DOI:10.1007/s10947-010-0058-3

2-(2-p-Tolyloxyethoxy)ethylchloroacetate is synthesized and its single crystal X-ray diffraction analysis is performed.

Full text of DOI:10.1007/s10947-010-0058-3

Journal of Structural Chemistry. Vol. 51, No. 2, pp. 392-394, 2010
Original Russian Text Copyright © 2010 by L. E. Foss, Yu. K. Voronina, P. I. Gryaznov,
A. T. Gubaidullin, P. S. Fakhretdinov, I. A. Litvinov, and G. V. Romanov
MOLECULAR AND CRYSTAL STRUCTURE OF 2-(2-p-
TOLYLOXYETHOXY)ETHYLCHLOROACETATE
L. E. Foss, Yu. K. Voronina, P. I. Gryaznov,
A. T. Gubaidullin, P. S. Fakhretdinov, I. A. Litvinov,
and G. V. Romanov
UDC 547.425.1:548.737
2-(2-p-Tolyloxyethoxy)ethylchloroacetate is synthesized and its single crystal X-ray diffraction analysis is
performed.
Keywords: 2-(2-p-tolyloxyethoxy)ethylchloroacetate, crystal and molecular structure, X-ray diffraction
analysis.
ꢀ-(Alkylaryloxy) ethylchloroacetates are the additives to lubricating oils [1a, b], plasticizers [1c], and feed stock for
2H-1,2-benzisothiazolin-3-one 1,1-dioxides that are used as intermediates for the synthesis of anti-inflammatory drugs [2].
Aryloxypoly(ethyleneoxy) chloroacetates [3] are the synthons for N-[alkylphenoxypoly(ethyleneoxy)carbonylmethyl]
heterylonium chlorides that possess bactericidal, virusocidal, and fungicidal activity and the properties of corrosion inhibitors
[4a], and N-[alkylphenoxypoly(ethyleneoxy) carbonylmethyl] ammonium and -morpholinium chlorides are regulating
additives of viscoelastic properties of crude oil systems [4b] and inhibitors of asphalt-tar-paraffin sediments in crude oil [4c].
ꢀ-(Alkylaryloxy)ethylchloroacetates were obtained by the condensation of chloroacetic acids and ꢀ-oxyphenetole
with chloric [1c, 5] or sulphuric acid [1b] as a catalyst. The acylation of 2-phenoxyethanol by monochloroacetic acid chloride
yields 2-phenoxyethylchloroacetate [2]. Aryloxypoly(ethyleneoxy)chloroacetates [3] were synthesized by the interaction of
aryloxypolyethylene glycols with chloroacetic acid in the presence of the H+-form of KU-2-8 cation-exchange resin as the
catalyst of heterogeneous catalysis.
ꢀ-[ꢀ-(Alkylphenoxy)ethoxy]ethyl ethers of chloroacetic acids have not been described so far. This work contains the
approach to obtain 2-(2-p-tolyloxyethoxy)ethylchloroacetate (3) by the interaction of 2-(2-p-tolyloxyethoxy)ethanol (1) with
monochloroacetic acid (2) in the presence of KU-2-8 cation-exchange resin as the catalyst.
The geometry of the molecule of 3 in the crystal is shown in Fig. 1ꢀ; the geometrical parameters are standard. The
packing of molecules in the crystal of compound 3 (Fig. 1b) represents the layers formed by C–H…ꢀ and ꢁ…ꢁ interactions
(Table 1). Within each layer the molecules are arranged so that it is possible to determine the hydrophilic and hydrophobic
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre, Russian Academy of Sciences;
pavelgr@iopc.ru. Translated from Zhurnal Strukturnoi Khimii, Vol. 51, No. 2, pp. 404-406, March-April, 2010. Original
article submitted March 25, 2009.
392
0022-4766/10/5102-0392 © 2010 Springer Science+Business Media, Inc.

Fig 1. Compound 3: a) molecule geometry in the crystal, b) molecule packing in
the crystal.
TABLE 1. ꢂ–ꢁ…ꢀ and *ꢂ–ꢁ…ꢁ Parameters of Interactions in the Crystal of Compound 3
Distance, Å
Angle, deg
D–H…A
Symmetric
transformation
Bond
H…A
D…A
C1–H12…O2
C3–H31…O6
x, 3/2–y, –1/2+z
x, 1/2–y, 1/2+z
x, 1/2–y, 1/2+z
x, 1/2–y, –1/2+z
x, 3/2–y, 1/2+z
2.49(2)
2.49(2)
2.54(2)
2.52(2)
3.2798(3)
3.4083(3)
3.3369(3)
3.249(3)
145(2)
162(2)
139(2)
C3–H32…O3
C12–H134…O4
*C6–H61…Cg(1)
129(2)
H…ꢂg = 2.74(2)
C–H…Cg = 151(1)
regions in each layer. The layers are distributed within the crystal so that hydrophilic and hydrophobic regions are separated
in the space. As expected based on the literature data, the benzene ring does not participate in NEP…ꢁ interactions. The
aromatic system of the benzene ring is characterized by ꢁ…ꢁ contacts that belong to weak hydrogen bonds [6, 7], which are
observed in the crystals of compound 3. These interactions have been studied extensively by now and their significance for
various chemical and biological systems has been shown. [8a-d]. However, ꢁ…ꢁ interactions are much weaker than C–
H…O hydrogen bonds that seem to be the structure forming elements in the crystals of compound 3.
1
Experimental. H NMR spectra were recorded on a Bruker Avance-600 spectrometer (600 MHz), IR spectra were
measured on a Bruker Vector-22 IR Fourier spectrometer.
2-(2-p-Tolyloxyethoxy)ethylchloroacetate 3. To 3.52 g 2-(2-p-tolyloxyethoxy)ethanol 1 in 7 ml absolute toluene
we added 1.77 g of monochloroacetic acid 2 in 7 ml toluene and 0.175 g KU-2-8 in the H+ form (5% 1 alcohol mass) in 10 ml
toluene. Azeotropic distillation was used to separate water; the catalyst was filtered; toluene was distilled, the residue was
also distilled; and we obtained 2.85 g (58.3%) ethylchloroacetate 3, b.p. 190-195ꢂꢂ (10 mm Hg), nD20 1.5125. Acetate 3
crystallized the next day, Tm 33-34ꢂꢂ. Found, %: C 57.04, H 6.11, Cl 13.27. C13H17ClO4. Calculated, %: C 57.25, H 6.24, Cl
13.03. 1ꢁ (CDCl3) NMR spectrum, ꢃ, ppm (J, Hz): 2.30 s (3H, CH3); 3.82 t [2H, 3JHH 4.9, CH2COC(O)]; 3.86 t (2H, 3JHH 4.9,
3
3
3
ArOCCH2); 4.08 s (2H, CH2Cl); 4.12 t (2H, JHH 4.9, ArOCH2); 4.38 t [2H, JHH 4.9, CH2OC(O)]; 6.83 d (2H, JHH 8.6,
ArCHo); 7.09 d (2H, 3JHH 8.6, ArCHm). IR spectrum, ꢄ, cm–1: 3031 (CAr–H, CH2–Cl); 2876-2953, and 1455 (CH3 ꢃ CH2); 1759
393

(C=O); 1512 (benzene ring); 1245 and 1039-1068 (CAr–O–CAlk); 1134-1179 (CAlk–O–CAlk); 820 (two adjacent hydrogen
atoms of the benzene ring); 703 (C–Cl) [9].
Crystallographic data for 3: formula C13H17ClO4, colorless prismatic crystals, formula weight 272.72 g mol–1,
monoclinic, a = 22.31(1) Å, b = 7.396(4) Å, c = 8.394(4) Å, ꢀ = 93.448(6)ꢂ, V = 1382.3(1) Å3, T = 293 K, space group P21/c,
Z = 4, μ(MoKꢅ) 2.8 cm–1, F(000) = 576, dx = 1.31 g4cm-3, 3017 reflections measured, 1788 unique. Final indices
R1(F) = 0.040, wR2(F2)= 0.0835 using 1788 reflections with I > 2ꢅ(I). Goodness-of-fit on F2 was 1.018,
27.00º, largest
max
diff. peak and hole 0.243 eÅ3 and –0.244 eÅ3.
X-Ray diffraction data for the crystals of compound 3 were collected at 293 K on a Bruker AXS Smart Apex II
CCD diffractometer in ꢆ and ꢇ-scan modes using graphite monochromated MoKꢅ (ꢆ 0.71073 Å) radiation. The data were
corrected for the absorption effect using the SADABS program [10]. The structures were solved by the direct method and
refined by the full matrix least-squares method using the SHELXL [12] and WinGX [13] programs. All non-hydrogen atoms
were refined anisotropically. All hydrogen atoms were located from the electron density difference synthesis and refined
isotropically. Data collections: images were indexed, integrated, and scaled using the APEX2 [11] data reduction package.
All figures were made using PLATON [14].
The crystallographic data (excluding structure factors) for structure 3 have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication numbers CCDC 724494. Copies of the data can be obtained, free
of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44-(0)1223-336033 or e-mail:
deposit@ccdc.cam.ac.uk).
REFERENCES
1. a) A. M. Kuliev, G. A. Zeinalova, and A. B. Kuliev, Author’s Certificate, USSR 232429 (1969); b) A. M. Kuliev,
G. A. Zeinalova, A. B. Kuliev, et al., Azerb. Khim. Zh., No. 3, 67-69 (1970); c) B. K. Zeinalov, A. B. Nasirov,
P. M. Kerimov, et al., Author’s Certificate, USSR 273189 (1970).
2. J. Svoboda, J. Palecek, and V. Dedek, Collect. Czechoslovak Chem. Commucat., 51, No. 6, 1304-1310 (1986).
3. P. S. Fakhretdinov, G. V. Romanov, O. V. Ugryumov, et al., Patent Application RF 98119862 (1998).
4. a) O. V. Ugryumov, O. A. Varnavskaya, V. N. Khlebnikov, et al., Patent RF 2220957 (2004); b) P. S. Fakhretdinov,
I. R. Mizipov, G. V. Romanov, et al., Patent RF 2221777 (2004); c) P. S. Fakhretdinov, G. V. Romanov, and
A. G. Romanov, Patent RF 2322435 (2008).
5. B. K. Zeinalov, A. B. Nasirov, P. M. Kerimov, and T. P. Gadzhiev, Uchen. Zap. Azerb. Univ., Ser. Khim. Nauk, No. 3,
51-53 (1972).
6. M. J. Tamres, J. Am. Chem. Soc., 74, 3375-3378 (1952).
7. M. M. Babu, Nucleic Acids Res., 31, 3345-3348 (2003).
8. a) M. Nishio, M. Hirota, and Y. Umezawa, The CH/p interaction. Evidence, Nature and Consequences, Wiley-VCH,
New York (1998); b) T. Steiner, Angew. Chem., 41, 48-76 (2002); c) T. Steiner and G. Koellner, J. Mol. Biol., 305,
535-557 (2001); d) E. A. Meyer, R. K. Castellano, and F. Diederich, Angew. Chem., 42, 1210-1250 (2003).
9. K. Nakanishi, Infrared Absorption Spectroscopy, Holden-Day, San Francisco (1962).
10. G. M. Sheldrick, SADABS, Program for Empirical X-Ray Absorption Correction, Bruker-Nonis (1990-2004).
11. APEX2 (Version 2.1), SAINTPlus. Data Reduction and Correction Program (Version 7.31A, Bruker Advansed X-ray
Solutions, BrukerAXS Inc., Madison, Wisconsin, USA (2006).
12. G. M. Sheldrick, SHELX-97, R97-2, Univ. Göttingen, Germany (1998).
13. L. J. Farrugia, WinGX 1.64.05 An Integrated System of Windows Programs for The Solution, Refinement and Analysis
of Single Crystal X-Ray Diffraction Data, J. Appl. Crystallogr., 32, 837/838 (1999).
14. A. L. Spek, PLATON for Windows Version 98., Acta Crystallogr., A46, No. 1, 34-41 (1990).
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