Abstract
C24H25ClN2O2, orthorhombic, P212121 (no. 19), a = 5.9066(2) Å, b = 15.7928(3) Å, c = 21.7829(6) Å, V = 2031.95(10) Å3, Z = 4, Rgt(F) = 0.0319, wRref(F2) = 0.0838, T = 150(2) K.
Show Summary Details
More options …
More options …
Zeitschrift für Kristallographie - New Crystal Structures
Editor-in-Chief: Huppertz, Hubert
Ed. by Reiß, Guido
6 Issues per year
IMPACT FACTOR 2016: 0.152
Cite Score 2016: 0.15
SCImago Journal Rank (SJR) 2016: 0.123
Source Normalized Impact per Paper (SNIP) 2016: 0.196
Crystal structure of 3-(2-(4-chlorophenyl)-3-hydroxy-3,3-diphenylpropyl)-1,1-dimethylurea, C24H25ClN2O2
Published Online: 2016-10-15 | DOI: https://doi.org/10.1515/ncrs-2016-0170
Open Access
This article offers supplementary material which is provided at the end of the article.
CCDC no.:: 1506294
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
3-(2-(4-Chlorophenyl)-3-hydroxy-3,3-diphenylpropyl)-1,1-dime thylurea was synthesized via double lithiation of 3-(2-(4-chlorophenyl)ethyl)-1,1-dimethylurea with excess tert-butyllithium (3.3 mole equivalents) at −60 °C in anhydrous tetrahydrofuran (THF) under an inert atmosphere. The dilithium reagent produced in-situ was allowed to react with a solution of benzophenone (2.2 mole equivalents) in THF, added via a syringe. The reaction mixture was stirred and allowed to warm up to room temperature over 2 h. Following work-up, the crude product was purified by column chromatography (silica gel) using a mixture of diethyl ether and hexane (1:3 by volume) to give the title compound (87%). Crystallization from a mixture of diethyl ether and ethyl acetate (4:1 by volume) gave colorless crystals, Mp 164–165 °C.
Experimental details
All hydrogen atoms were placed in calculated positions and refined using a riding model. Methyl C—H bonds were fixed at 0.98 Å and the groups were allowed to spin about the C—C bond with displacement parameters 1.5 times Ueq(C). Aromatic C—H distances were set to 0.95 Å and N—H set to 0.88 Å with Uiso set to 1.2 times the Ueq for the atoms to which they are bonded.
Discussion
Urea derivatives show various biological activities [1], [2], [3], [4]. They can be synthesized efficiently in high yields using simple procedures [4], [5], [6], [7]. Aromatic substituted ureas can be further easily substituted via lithiation followed by reactions with electrophiles [8], [9], [10], [11], [12].
In the crystal structure, the asymmetric unit comprises one molecule of C24H25ClN2O2. An intramolecular O—H⋯O hydrogen bond is observed in the molecule with an O2⋯O1 distance of 2.732(3) Å and O2—H2⋯O1 angle of 161.7°. Two weak intermolecular C—H⋯Cl interactions occur in the crystal structure (with geometry: C2⋯Cl1 = 3.806(3) Å, C2—H2a⋯Cl1 = 153.9° and C2⋯Cl1 = 3.733(3) Å, C2—H2b⋯Cl1 = 158.4°) leading to the formation of molecular chains along [100]. The structure is racemically twinned.
Acknowledgements
This project was supported by the Deanship of Scientific Research at Prince Sattam bin Abdulaziz University under the research project 2015/01/5162 and thanks are also due to Cardiff University for continued support.
References
- 1.
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
- 2.
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
- 3.
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. Chem. Med. Chem. 6 (2011) 1680–1692. Google Scholar
- 4.
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
- 5.
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
- 6.
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
- 7.
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
- 8.
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
- 9.
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
- 10.
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
- 11.
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
- 12.
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
- 13.
Agilent. CrysAlisPRO. Agilent Technologies, Yarnton, England, (2014). Google Scholar
- 14.
Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122. Google Scholar
- 15.
Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl. Crystallogr. 45 (2012) 849–854. Google Scholar
- 16.
Cambridge Soft. CHEMDRAW Ultra. Cambridge Soft Corporation, Cambridge, Massachusetts, USA, (2001).Google Scholar
About the article
Received: 2016-05-26
Accepted: 2016-09-26
Published Online: 2016-10-15
Published in Print: 2017-01-01
Funding Source: Prince Sattam bin Abdulaziz University
Award identifier / Grant number: 2015/01/5162
This project was supported by the Deanship of Scientific Research at Prince Sattam bin Abdulaziz University under the research project 2015/01/5162 and thanks are also due to Cardiff University for continued support.
Citation Information: Zeitschrift für Kristallographie - New Crystal Structures, Volume 232, Issue 1, Pages 101–103, ISSN (Online) 2197-4578, ISSN (Print) 1433-7266, DOI: https://doi.org/10.1515/ncrs-2016-0170.
©2016 Mohammed B. Alshammari 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
Comments (0)