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One-pot Synthesis of 5,7-Diaryl-3,4,6-trihydronaphthalen-2-ones
One-pot Synthesis of 5,7-Diaryl-3,4,6-trihydronaphthalen-2-ones
Journal of the Korean Chemical Society. 2007. Aug, 51(4): 356-360
Copyright © 2007, The Korean Chemical Society
  • Received : April 03, 2007
  • Published : August 20, 2007
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About the Authors
M. Gopalakrishnan
H. Manikandan
P. Sureshkumar
J. Thanusu
V. Kanagarajan

Abstract
5,7-Diaryl-3,4,6-trihydronaphthalen-2-ones have been synthesized from 3,5-diaryl-cyclohex-2-en-1-ones and methyl vinyl ketone in the presence of sodium ethoxide. The products were characterized by IR, UV-Visible, 1 H-NMR, 13 C-NMR and mass spectral techniques. To confirm 1 H and 13 C signals, HSQC spectrum was recorded and analyzed.
Keywords
INTRODUCTION
Michael reaction 1 is the nucleophilic addition of a carbanion, formed from compounds containing active methylene group to an alpha-beta unsaturated ketone 2 , ester 1 , nitrile 3 , etc. There is a general interest in the synthesis of bicyclic ketone because this structural unit is the main function of various natural fragments. It is a versatile intermediate in the synthesis of various steroids and hormones. A tandem reaction comprising a Michael addition step followed by an aldol condensation to produce a cyclic compound is Robinson annulation 4 - 9 . It is an useful method for the synthesis of natural products consisting of fused ring systems such as terpenes and alkaloids 10 . Robinson annulation can be performed under catalytic conditions using La(OiPr) 3 -MS 4A 11 , Al 2 O 3 12 , S-proline 13 , and AB38C2 14 . Moreover, solvent-free Robinson annulation with sodium ethoxide 15 was also performed. It can also be effected in onepot using acid catalysts 16 , 17 . In this paper, we report synthesis of some 5,7-diaryl-3,4,6-trihydronaphthalen-2-ones.
RESULTS AND DISCUSSION
Some 5,7-diaryl-3,4,6-trihydronaphthalen-2-ones were synthesized from 3,5-diarylcyclohex-2-en-1-ones and methyl vinyl ketone in the presence of sodium ethoxide. The products were characterized on the basis of their IR, UV-visible, 1 H NMR, 13 C NMR and Mass spectral studies. To confirm the 1 H and 13 C NMR spectral assignments, HSQC spectrum was recorded for 5a and analyzed. All the spectral studies along with TLC indication bear evidence that the formed products are 5a-c. The compounds were isolated by column chromatography using petroleum ether-benzene (1:4) mixture as an eluent system. Attempts to isolate 3a-c and 4a-c were unsuccessful. The schematic representation describing the route of synthesis is furnished in 1 .
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Synthesis of some 5,7-diaryl-3,4,6-trihydronaphthalen-2-ones.
The IR-spectrum of 5a showed one strong carbonyl absorption at 1638 cm -1 assignable to a cyclic α,β-unsaturated ketone stretching frequency. The IR spectrum of 1a showed carbonyl absorption at 1653 cm -1 . 5a is also a α,β-unsaturated ketone but it has a frequency of 1638 cm -1 , which is lower than the stretching frequency of 1a , is due to extended conjugation.
In the GC-MS spectrum of 5a , the observed single peak confirms its formation as a sole product. In the mass spectrum the molecular ion peak observed at 298 is also an additional evidence for the formation of 5a. The other important fragment peaks are 270, 229, 144, 116, 115, 91, 76 and 54, which agree with the fragment pattern of 2-naphthol. The plausible fragmentation pattern is given in 1 .
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Fragmentation pattern for 5,7-diphenyl-3,4,6-trihydronaphthalen-2-one.
The UV-visible spectrum of 5a shows two major absorptions at 248 nm and 288 nm. The λ max at 248 nm is due to π-π∗ transition of phenyl substituent. The other λ max at 288 nm may be due to the unsaturated ketone. The calculated λ max value 297 nm is almost equivalent to the observed λ max value. If the compound 5a is a saturated one, then the λ max value should be around 250 nm. But in the case under study λ max is 288 nm which is adequate confirmation of the fact that 5a is unsaturated.
The complete 1 H and 13 C NMR spectral assignments for the products 5a-c are given in the experimental section.
- Analysis of HSQC Spectrum
To confirm the 1 H-NMR and 13 C-NMR signals of 5a , HSQC spectrum was recorded and is given in 1 . It shows eight cross peaks, which are analyzed as follows: The cross peaks 1 and 2 reveal that the protons are connected to carbon signal at 36 ppm. The signal for the C-4 carbon appears as two signals at 3 and 2.9 ppm. The third cross peak is connected to a carbon signal at 41.5 ppm. C-3 carbon, which appeared at 41.5 ppm, is connected to proton at 3.4 ppm. Hence the signal at 3.4 ppm is conveniently assigned to H-3 proton.
The fourth cross peak is connected to a carbon signal at 44.3 ppm, which is connected to C-6 carbon and two proton signals at 2.9 and 2.7 ppm. Hence the signals at 2.9 and 2.7 ppm are assigned to two H-6 protons.
The fifth cross peak is connected to 7.01 ppm of 1 H signal and 113.6 ppm of 13 C signal. The seventh cross peak is connected to 6.47 ppm of 1 H signal and 125.4 ppm of 13 C signal. The fifth and seventh cross peaks may be due to C-8 and C-1 carbons and its protons respectively. The proton signals at 7.01 and 6.47 ppm are assigned to H-1 and H-8, respectively. The eighth cross peak appears as a cluster that is connecting the carbon signals at aromatic region and its protons.
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- Experimental Section
Melting points of the compounds were recorded on an electro-thermal apparatus and are uncorrected. IR-spectra in KBr were recorded in NICOLET AVATAR-330-FT-IR spectrophotometer. UVvisible spectrum was recorded on HITACHI-U-2001 double beam spectrophotometer. 1 H NMR spectra were recorded on BRUKER AMX-400 spectrometer operating at 400 MHz. 13 C NMR spectra were recorded on BRUKER AMX-400 spectrometer at operating frequency 100 MHz. The mass spectra were recorded on VG-MICROMASS-7070F double mass spectrometer. The HSQC was recorded on BRUKER AMX-400 spectrometer. The purity of the compounds was checked on TLC.
The chalcones were prepared according to the literature 18 . 3,5-Diaryl-cyclohex-2-en-1-ones [ 1a-c ] were prepared by adopting the literature procedure 19 .
- Preparation of 5,7-Diaryl-3,4,6-trihydronaphthalen-2-one 5a:
A solution of sodium ethoxide was prepared from 0.01 g of freshly cut sodium and 10 ml ethanol in a round-bottomed flask. To this, 3,5-Diphenylcyclohex-2-en-1-one (0.248 g) 1a in absolute ethanol (20 ml) was added and stirred for one hour at room temperature. To this mixture methyl vinyl ketone (0.1 ml) in absolute alcohol (10 ml) was added and the stirring was continued for over night. To the reaction mixture, 100 ml of CHCl 3 followed by ice water were added. The organic phase was separated, washed with brine and dried over anhydrous sodium sulphate. The residue, obtained after evaporation of the solvent was subjected to column chromatography using petroleum ether-benzene (1:4) as an eluent mixture to afford 5a. Yield: 55%; m.p. 96-98˚C; MS: C 22 H 18 O; m/z: 298 (M +• ), 270, 229, 144, 116, 115, 102, 91, 76, 52; IR cm -1 : 3052, 1638, 1590, 1573, 1495, 1446, 761, 697; UV nm: 248, 288; 1 H NMR, CDCl 3 , δ ppm: 2.60-2.78 (m, 2H, H 6 ); 2.83-2.91 (m, 1 H, H 4a ); 3.01 (dd, 1 H, H 4e ); 3.36-3.44 (m, 2H, H 3 ); 6.47 (s, 1H, H 1 ); 7.01 (s, 1 H, H 8 ); 7.21-7.56 (m, 10H, Ar-H’s); 13 C-NMR, CDCl 3 δ ppm: 200.2 (C-2); 159.7 (C-7); 157.2 (C-5); 113.6 (C-8); 125.4 (C-1); 44.3 (C-6); 41.5 (C-3); 36.7 (C-4); 138.7-143.7 (C-9, C-10 and two ipso carbons); 125.4-130.7 Ar-C’s.
Compounds 5b and 5c were synthesized similarly.
- 5-(4'-Methylphenyl)-7-phenyl-3,4,6-trihydronaphthalen-2-one 5b:
Yield: 50%; m.p.: 102-104°C; MS: C 23 H 20 O; m/z: 312 (M +• ), 284, 243, 144, 116, 115, 102, 91, 76, 52; IR cm -1 : 3050, 2973, 1630, 1585, 1570, 1490, 1440, 1375, 756, 693; 1 H NMR, CDCl 3 , δ ppm: 2.62-2.88 (m, 2H, H 6 ), 3.02 (dd, 1 H, H 4e ), 2.86-2.99 (m, 2H, H 4a ), 3.38-3.49 (m,2H,H 3 ), 2.40 (s, 3H, CH 3 at phenyl ring), 6.52 (s, 1H, H 1 ), 7.08 (s, 1H, H 8 ); 7.60-7.24 (m, 10H, Ar-H’s); 13 C NMR CDCl 3 δ ppm: 124.5 (C-1); 201.4 (C-2); 42.1 (C-3); 37.3 (C-4); 160.3 (C-5); 44.5 (C-6); 157.8 (C-7); 114.1 (C-8); 21.5 (CH 3 at Phenyl ring); 137.6 (C-CH 3 ); 139.2-144.2 (C-9, C-10 and two ipso carbons); 129.7-125.9 (Ar-C’s).
- 5-(4'-Methoxyphenyl)-7-phenyl-3,4,6-trihydronaphthalen-2-one 5c:
Yield: 52%; m.p.: 106-108°C; MS: C 23 H 20 O 2 ; m/z: 328 (M +• ), 300, 259, 144, 116, 115, 102, 91, 76, 52.; IR cm -1 : 3042, 1632, 1587, 1572, 1492, 1446, 1265, 1248, 759, 695; 1 H NMR CDCl 3 δ ppm: 2.55-2.72 (m, 2H, H 6 ), 2.78-2.85 (m, 2H, H 4a ), 2.97 (dd, 1H, H 4e ), 3.31-3.38 (m, 2H, H 3 ), 3.95 (s, 3H, OCH 3 at phenyl ring); 6.41 (s, 1H, H-1), 7.12 (s, 1H, H 8 ) 7.10-7.56 (m, 9H, Ar-H’s); 13 C NMR CDCl 3 δ ppm: 200.9 (C-2); 124.7 (C-1); 41.0 (C-3); 36.2 (C-4); 159.3 (C-5); 43.9 (C-6); 55.4 (OCH 3 at phenyl ring); 156.7 (C-7); 113.9 (C-8); 143.1-138.1 (C-9, C-10 and two ipso carbons); 159.2 (C-OCH 3 ); 124.9-128.9 (Ar-C’s).
Acknowledgements
We wish to thank NMR Research Centre, (Sophisticated Instruments Facility), IISc, Bangalore, India for recording NMR spectra.
References
Michael J. 1887 J. Perakt, Chem. 35 251 -
Kohler A. 1907 Am. Chem. J. 37 385 -
Vorlander S. 1902 Ann. 66 320 -
Du Feu E. C. , Mc Quillin F. J. , Robinson R. 1937 J. Chem. Soc. 53 -    DOI : 10.1039/jr9370000053
Balasubramanian K. , John J. P. , Swaminathan S. 1974 Synthesis 51 -    DOI : 10.1055/s-1974-23240
Bergmann E. D. , Gingberg D. , Pappo R. 1959 Org. React. 10 179 -
Trost B. M. , Fleming I. 1991 Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency in Modern Organic Chemistry, 2 Pergamonn Press New York 4 -
Rapson W. S. , Robinson R. 1935 J. Chem. Soc. 1285 -    DOI : 10.1039/jr9350001285
Ramachandran S. , Newmann M. S. 1973 Organic Synthesis, 5 John Wiley and Sons, Inc NewYork 486 -
Ho L.C. 1988 Carbocycle Construction in Terpene Synthesis VCH Publishers Inc NewYork
Okano T. , Satou Y. , Tamura M. , Kiji J. 1997 Bull. Chem. Soc. Jpn. 70 1879 -    DOI : 10.1246/bcsj.70.1879
Takatori K. , Nakayama M. , Yamada N. , Hirayam S. , Kasiwara M. 2003 Chem. Pharm. Bull. 4 455 -    DOI : 10.1248/cpb.51.455
Rajagopal D. , Narayanan R. , Swaminathan S. 2001 Proc. Indian Acad. Sci. (Chem. Sci.) 113 197 -    DOI : 10.1007/BF02704070
Zhong G. , Hoffmann T. , Lerner R. A. , Danishefsky S. , Barbas C. F. 1997 J. Am. Chem. Soc. 119 8131 -    DOI : 10.1021/ja970944x
Miyamoto H. , Kanetaka S. , Tanaka K. , Yoshizawa , Toyota S. , Toda F. 2000 Chem. Lett. 888 -    DOI : 10.1246/cl.2000.888
Heathcock C. H. , Ellis J. E. , Mc Murry , Cappolino A. 1971 Tetrahedron Lett. 12 4995 -    DOI : 10.1016/S0040-4039(01)97609-9
Heathcock C. H. , Mahaim C. , Schlecht M. F. , Utawanit T. 1984 J. Org. Chem. 49 3264 -    DOI : 10.1021/jo00192a004
Furniss B. S. , Hannaford A. J. , Smith P. G. , Tatchell A. R. 1997 Vogel’s textbook of practical organic chemistry” 5th ed. ELBS 1033 -
Balasubramanian M. , Souza A. D. 1968 Tetrahedron 24 5399 -    DOI : 10.1016/S0040-4020(01)96334-3