Advanced
Synthesis of Substituted Biarylmethanol via Ferrocenyloxime Palladacycles Catalyzed Suzuki Reaction of Chlorophenylmethanol in Water
Synthesis of Substituted Biarylmethanol via Ferrocenyloxime Palladacycles Catalyzed Suzuki Reaction of Chlorophenylmethanol in Water
Bulletin of the Korean Chemical Society. 2014. Aug, 35(8): 2551-2554
Copyright © 2014, Korea Chemical Society
  • Received : March 11, 2014
  • Accepted : April 09, 2014
  • Published : August 20, 2014
Download
PDF
e-PUB
PubReader
PPT
Export by style
Article
Author
Metrics
Cited by
TagCloud
About the Authors
Hong-Mei Li
Ai-Qing Feng
Xin-Hua Lou
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471022, China

Abstract
Keywords
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
Experimental
Materials and Measurement. The chloride-bridged palladacyclic dimer 1 was prepared according to published procedures. 18 All other chemicals were used as purchased. Elemental analyses were determined with a Thermo Flash EA 1112 elemental analyzer. IR spectra were collected on a Bruker VECTOR22 spectrophotometer using KBr pellets. NMR spectra were recorded on a Bruker DPX-400 spectrometer in CDCl 3 with TMS as an internal standard. Mass spectra were measured on a LC-MSD-Trap-XCT instrument. Crystallographic data were collected on a Bruker SMART APEX-II CCD diffractometer. CCDC reference number 625798 for 2 . The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc. cam.ac.uk/data_request/cif.
[PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-C(CH3)=NOH](DCPAB)] (2): A solution of 1 (0.1 mmol) and DCPAB (0.20 mmol) in CH 2 Cl 2 (10 mL) was stirred at room temperature for 30 min. The product was separated by passing through a short silicagel column with CH 2 Cl 2 /ethyl acetate (1:1, v/v) as eluent. The second band was collected and afforded complex 2 . Red solid, 89% yield. Found: C, 58.92; H, 6.10; N 3.92. Calc. for C 38 H 48 ClFeN 2 OPPd: C, 58.70; H, 6.22; N, 3.73%. IR (KBr, cm −1 ): 2925, 2851, 1599 (C=N), 1447, 1315, 1264, 1106, 1052, 1002, 808, 752. 1 H NMR (400 MHz, CDCl 3 ) δ 9.89 (1H, brs, OH), 7.98 (1H, m, ArH), 7.21-7.37 (5H, m, ArH), 7.04-7.09 (2H, m, ArH), 4.24 (1H, s, C 5 H 3 ), 4.07-4.14 (6H, m, C 5 H 5 +C 5 H 3 ), 3.92 (1H, s, C5H3), 2.56 (3H, s, CH 3 ), 2.51 (3H, s, CH 3 ), 2.17 (3H, s, CH 3 ), 2.35 (2H, m, PCy2), 1.76-1.06 (20H, m, Cy). 31 P{ 1 H}NMR (162 MHz, CDCl 3 ) δ 67.15, 65.54. MS-ESI + [ m/z ]: 741.2 (M + -Cl).
General Procedure for the Coupling Reaction of Chlorophenylmethanol. In a Schlenk tube, a mixture of the prescribed amount of catalyst, aryl halides (1.0 mmol), aryl boronic acids (1.5 mmol) and the selected base (2.0 mmol) in water was evacuated and charged with nitrogen. The reaction mixture was heated at 100 °C for 24 h. After being cooled, the mixture was extracted with CH 2 Cl 2 and evaporated, the resulting residue was purified by flash chromatography on silica gel using mixture of CH 2 Cl 2 /ethyl acetate (5/1) as eluent. The products 4b, 4d and 4j were determined by 1 H and C 13 NMR. Other products were characterized by comparison of data with those in the literature. 17,19
4′-Phenyl-biphenyl-2-methanol (4b): Yield 75%. 1 H NMR (400 MHz, CDCl 3 ) δ 8.22-8.29 (m, 3H, ArH), 7.76 (m, 2H, ArH), 7.40-7.49 (m, 3H, ArH), 7.40-7.49 (m, 4H, ArH), 7.29 (d, 1H, ArH), 4.60 (s, 2H, CH 2 ), 1.68 (s, 1H, OH). 13 C NMR (100 MHz, CDCl3) δ 141.0, 140.7, 140.1, 139.6, 138.1, 130.1, 129.7, 129.1, 128.9, 128.6, 128.4, 127.8, 127.5, 127.1, 63.3. MS-ESI + [ m/z ]: 260.1 (M + ). Anal. Calc. for C 19 H 16 O: C, 87.66; H, 6.19. Found: C, 87.85; H, 6.07.
4′-Ethyl-biphenyl-2-methanol (4d): Yield 87%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.52-7.55 (m, 1H, ArH), 7.23-7.39 (m, 7H, ArH), 4.61 (s, 2H, CH 2 ), 2.70 (q, 2H, CH2), 1.71 (s, 1H, OH), 1.28 (t, 3H, CH 3 ). 13 C NMR (100 MHz, CDCl 3 ) δ 143.3, 141.3, 138.1, 137.9, 130.2, 129.1, 128.9, 128.4, 127.8, 127.6, 62.9, 29.7, 15.6. MS-ESI + [ m/z ]: 212.1 (M + ). Anal. Calc. for C 15 H 16 O: C, 84.87; H, 7.60. Found: C, 84.99; H, 7.46.
3′-Nitro-biphenyl-2-methanol (4j): Yield 74%. 1 H NMR (400 MHz, CDCl 3 ) δ 7.63-7.66 (m, 2H, ArH), 7.55-7.59 (m, 1H, ArH), 7.32-7.48 (m, 5H, ArH), 4.66 (s, 2H, CH 2 ), 1.72 (s, 1H, OH). 13 C NMR (100 MHz, CDCl 3 ) δ 148.1, 142.3, 139.1, 137.8, 135.4, 130.0, 129.2, 129.1, 128.8, 128.2, 124.1, 122.3, 63.0. MS-ESI + [ m/z ]: 229.1 (M + ). Anal. Calc. for C 13 H 11 NO 3 : C, 68.11; H, 4.84; N, 6.11. Found: C, 68.34; H, 4.72; N, 6.27
Acknowledgements
This work was supported by the National Science Foundation of China (No. 21272110), the Aid Project for the Leading Young Teachers in Henan Provincial Institutions of Higher Education of China (2013GGJS-151) and the Science Foundation of Henan Education Department (14A150049).
References
Tojo G. , Fernández M 2006 Oxidation of Alcohols to Aldehydes and Ketones Springer New York
Caron S. , Dugger R. W. , Ruggeri S. G. , Ragan J. A. , Ripin D. H. B. 2006 Chem. Rev. 106 2943 -    DOI : 10.1021/cr040679f
Miyaura N. , Suzuki A. 1995 Chem. Rev. 95 2457 -    DOI : 10.1021/cr00039a007
Dupont J. , Pfeffer M 2008 Palladacycles Wiley-VCH Weinheim
Li H. M. , Xu C. , Hao X. Q. , Li Z. , Wang Z. Q. , Fu W. J. , Song M. P. 2013 Inorg. Chim. Acta 404 236 -    DOI : 10.1016/j.ica.2013.04.014
Broadhead D. G. , Osgerby J. M. , Pauson P. L. 1958 J. Chem. Soc. 650 -    DOI : 10.1039/jr9580000650
Braga D. , Grepioni F. , Tedesco E. 1997 Organometallics 16 1846 -    DOI : 10.1021/om9608364
López C. , Bosque R. , Solans X. , Font-Bardía M. 1997 J. Organomet. Chem. 539 99 -    DOI : 10.1016/S0022-328X(97)00030-2