Abstract
C10H14N2O2, monoclinic, P21/c (no. 14), a = 14.9185(12) Å, b = 7.7243(6) Å, c = 9.2229(5) Å, β = 91.032(6)°, V = 1062.63(13) Å3, Z = 4, T = 293(2) K.
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Zeitschrift für Kristallographie - New Crystal Structures
Editor-in-Chief: Huppertz, Hubert
Ed. by Reiß, Guido
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Crystal structure of 1,1-dimethyl-3-(4-methoxyphenyl)urea, C10H14N2O2
Published Online: 2017-01-20 | DOI: https://doi.org/10.1515/ncrs-2016-0238
Open Access
This article offers supplementary material which is provided at the end of the article.
CCDC no.:: 1525571
The asymmetric unit of the title crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Table 1
Data collection and handling.
Table 2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
Source of material
To a stirred solution of triphosgene (1.0 mole equivalent) in dichloromethane (DCM), a solution of 4-methoxyaniline (2.5 mole equivalents) and triethylamine (5.5 mole equivalents) in DCM was slowly added over 30 min at 0 °C. The mixture was stirred at 0 °C for 2 h, after which a solution of dimethylamine (3.0 mole equivalents) in tetrahydrofuran was added. The reaction mixture was stirred at 0 °C for 1 h. The mixture was poured onto water and the DCM layer was separated, washed with water, and dried over magnesium sulfate and the solvent was then removed under reduced pressure. Crystallization of the obtained raw solid using a mixture of ethyl acetate and diethyl ether (1:3 by volume) gave the title compound, 1,1-dimethyl-3-(4-methoxyphenyl)urea (83%) as colorless crystals, Mp. 132–133 °C (lit. 131–132 °C [1]).
Experimental details
Non-hydrogen atoms were refined with anisotropic displacement parameters. The N-H proton was refined freely but all other hydrogen atoms were placed in calculated positions and refined using a riding model. C-H bonds of the methyl groups were fixed at 0.96 Å, with displacement parameters 1.5 times Ueq(C) for the hydrogen atoms, and were allowed to spin about the C-C bond. Aromatic C-H distances were set to 0.93 Å and their U(iso) values of the corresponding hydrogen atoms were set to 1.2 times the Ueq values of the atoms to which they are bonded.
Comment
Many urea derivatives are very important intermediates in organic syntheses and show a variety of biological activities [2], [3], [4], [5]. Various efficient procedures for the synthesis of aromatic ureas are known [6], [7], [8], [9], [10], [11]. Aromatic ureas can be easily modified via treatment with lithium reagents followed by reactions with electrophiles, a methodology we have used in the last few years [12], [13], [14], [15], [16].
The asymmetric unit contains one molecule of C10H14N2O2. In the molecule, the methoxybenzene group is almost planar with a C3—C4—O2—C10 torsion angle of 7.5(4)°. The rest of the molecule is not planar with twist angles 46.90(9)° between the phenyl and the NC(O)N groups and 10.68(34)° between NC(O)N and N(Me2) groups. In the crystal, N-H⋯O hydrogen bonding is observed with geometry: N1—H1⋯O1 = 158(2)°, N1⋯O1 = 2.966(2) Å. The hydrogen bonds construct chains of molecules along [001]. All bond lengths and angles are in the expected ranges.
Acknowledgement
The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for its funding for this research through the research group project RGP-239 and to Cardiff University for the continued support.
References
- 1
Hutchby, M.: Novel Synthetic Chemistry of Ureas and Amides. Springer Thesis, Springer, 2013. Google Scholar
- 2
Chen, J.-N.; Wang, X.-F.; Li, T.; Wu, D.-W.; Fu, X.-B.; Zhang, G.-J.; Shen, X.-C.; Wang, H.-S.: Design, synthesis, and biological evaluation of novel quinazolinyl-diaryl urea derivatives as potential anticancer agents. Eur. J. Med. Chem. 107 (2016) 12–25. Google Scholar
- 3
Kocyigit-Kaymakcioglu, B.; Celen, A. O.; Tabanca, N.; Ali, A.; Khan, S. I.; Khan, I. A.; Wedge, D. E.: Synthesis and biological activity of substituted urea and thiourea derivatives containing 1,2,4-triazole moieties. Molecules 18 (2013) 3562–3576. Google Scholar
- 4
Gennäs, G. B.; Mologni, L.; Ahmed, S.; Rajaratnam, M.; Marin, O.; Lindholm, N.; Viltadi, M.; Gambacorti-Passerini, C.; Scapozza, L.; Yli-Kauhaluoma, J.: Design, synthesis, and biological activity of urea derivatives as anaplastic lymphoma kinase inhibitors. ChemMedChem 6 (2011) 1680–1692. Google Scholar
- 5
Wilson, A. A.; Garcia, A.; Houle, S.; Sadovski, O.; Vasdev, N.: Synthesis and application of isocyanates radiolabeled with carbon-11. Chem. Eur. J. 17 (2011) 259–264. Web of ScienceGoogle Scholar
- 6
Thalluri, K.; Manne, S. R.; Dev, D.; Mandal, B.: Ethyl 2-cyano-2-(4-nitrophenylsulfonyloxyimino)acetate-mediated Lossen rearrangement: single-pot racemization-free synthesis of hydroxamic acids and ureas from carboxylic acids. J. Org. Chem. 79 (2014) 3765–3775. Google Scholar
- 7
Carnaroglio, D.; Martina, K.; Palmisano, G.; Penoni, A.; Domini, C.; Cravotto, G.: One-pot sequential synthesis of isocyanates and urea derivatives via a microwave-assisted Staudinger–aza-Wittig reaction. Beilstein J. Org. Chem. 9 (2013) 2378–2386. Google Scholar
- 8
Vinogradova, E. V.; Fors, B. P.; Buchwald, S. L.: Palladium-catalyzed cross-coupling of aryl chlorides and triflates with sodium cyanate: a practical synthesis of unsymmetrical ureas. J. Am. Chem. Soc. 134 (2012) 11132–11135. Google Scholar
- 9
Wu, C.; Cheng, H.; Liu, R.; Wang, Q.; Hao, Y.; Yu, Y.; Zhao, F.: Synthesis of urea derivatives from amines and CO2 in the absence of catalyst and Solvent. Green Chem. 12 (2010) 1811–1816. Google Scholar
- 10
Mizuno, T.; Nakai, T.; Mihara, M.: Synthesis of unsymmetrical ureas by sulfur-assisted carbonylation with carbon monoxide and oxidation with molecular oxygen under mild conditions. Synthesis 41 (2009) 2492–2496. Google Scholar
- 11
Artuso, E.; Degani, I.; Fochi, R.; Magistris, C.: Preparation of mono-, di-, and trisubstituted ureas by carbonylation of aliphatic amines with S,S-dimethyl dithiocarbonate. Synthesis 39 (2007) 3497–3506. Google Scholar
- 12
Smith, K.; El-Hiti, G. A.; Alshammari, M. B.: Directed lithiation of N′-(2-(4-methoxyphenyl)ethyl)-N,N-dimethylurea and tert-butyl (2-(4-methoxyphenyl)ethyl)carbamate. Synthesis 46 (2014) 394–402. Google Scholar
- 13
Smith, K.; El-Hiti, G. A.; Alshammari, M. B.: Control of site of lithiation of 3-(aminomethyl)pyridine derivatives. Synthesis 45 (2013) 3426–3434. Google Scholar
- 14
Smith, K.; El-Hiti, G. A.; Alshammari, M. B.: Lithiation and substitution of N′-(ω-phenylalkyl)-N,N-dimethylureas. Synthesis 44 (2012) 20139–2022. Google Scholar
- 15
Smith, K.; El-Hiti, G. A.; Alshammari, M. B.: Variation in the site of lithiation of 2-(2-methylphenyl)ethanamine derivatives. J. Org. Chem. 77 (2012) 11210–11215. Google Scholar
- 16
Smith, K.; El-Hiti, G. A.; Hegazy, A. S.: Lateral lithiation of N′-(2-methylbenzyl)-N,N-dimethylurea and N-(2-methylbenzyl)pivalamide: Synthesis of tetrahydroisoquinolines. Synthesis 42 (2010) 1371–1380. Google Scholar
- 17
Agilent. CrysAlisPRO. Agilent Technologies, Yarnton, England, 2014. Google Scholar
- 18
Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122. Google Scholar
- 19
Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl. Crystallogr. 45 (2012) 849–854. Google Scholar
- 20
Cambridge Soft. CHEMDRAW Ultra. Cambridge Soft Corporation, Cambridge, Massachusetts, USA, 2001. Google Scholar
About the article
Received: 2016-08-02
Accepted: 2017-01-04
Published Online: 2017-01-20
Published in Print: 2017-03-01
Citation Information: Zeitschrift für Kristallographie - New Crystal Structures, Volume 232, Issue 2, Pages 279–281, ISSN (Online) 2197-4578, ISSN (Print) 1433-7266, DOI: https://doi.org/10.1515/ncrs-2016-0238.
©2017 Gamal A. El-Hiti et al., published by De Gruyter.. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. BY-NC-ND 3.0
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