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PEG-Mediated Catalyst-Free Expeditious Synthesis of Functionalized Benzene/Biaryl and Fluoren-9-one Derivatives from Activated Acetylenes and 1,3-Diones
PEG-Mediated Catalyst-Free Expeditious Synthesis of Functionalized Benzene/Biaryl and Fluoren-9-one Derivatives from Activated Acetylenes and 1,3-Diones
Journal of the Korean Chemical Society. 2012. Jun, 56(3): 316-321
Copyright © 2012, The Korean Chemical Society
  • Received : November 30, 2011
  • Accepted : April 09, 2012
  • Published : June 20, 2012
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About the Authors
Mohammad Piltan
mohammadpiltan@yahoo.com
Issa Yavari
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran
Loghman Moradi
Department of Chemistry, University of Kurdistan, Sanandaj, Iran
Seyed Amir Zarei

Abstract
Poly(ethylene glycol) (PEG) has been used as a sustainable, non-volatile, and environmentally friendly reaction solvent for the synthesis of functionalized benzene/biaryl and fluoren-9-one derivatives from activated acetylenes and 1,3-diones at 100 ℃. No additional solvent and catalyst are required.
Keywords
INTRODUCTION
As useful compounds in organic chemistry and natural product chemistry, polysubstituted benzenes play important roles in medicinal chemistry. 1 Biaryls are beneficial as components in new organic materials like electroluminescent conjugated polymers, 2 semiconductors, and liquid crystals. 3 The quest to develop efficient and versatile methods for the synthesis of substituted benzenes and biaryls has been a perennial theme in organic synthesis. The Friedel-Crafts reaction 4 and the ortho -metallation strategy 5 can be used for introducing substituents into the benzene ring. The Reppe reaction, 6 the Vollhardt protocol, 7 , 8 and the Bergman cyclization 9 have hold many promises for the synthesis of substituted benzenes.
Fluoren-9-ones are an important class of carbocycle because of their significant role in pharmaceutical applications, 10 as photosensitizers, 11 and their use as the key intermediates in organic synthesis. 12 A number of fluoren-9- one natural products, including dengibsin, dengibsinin, and dendroflorin, have recently been reported to occur in the Asiatic orchid Dendrobium gibsonii Lindley ( 1 ). 13
Tilorone, (2,7-bis[2-(diethylamino)ethoxy]-9 H -fluoren-9-one, 2 ), was the first low-molecular weight IFN-inducer orally effective in vivo against some DNA and RNA viruses. 14 , 15
Carbapenem L-742,728 is a 9 H -fluoren-9-one derivative and has been reported as an anti-Methicillin-Resistant Staphylococcus Aureus (MRSA) agent ( 2 ). 16
Recently, PEG has been found to be an interesting solvent system. The important difference between using PEG and other neoteric solvents are that all the toxicological properties, the short- and long-term hazards, and the biodegradability, etc., are established and known. The application of PEG as a reaction medium is highly beneficial as the system remains neutral, which helps in maintaining a wide variety of functional groups unchanged that is either acid or base susceptible. 17
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Structure of some fluoren-9-one natural products.
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Structure of some synthesized fluorenone derivatives.
Recently, the synthesis of polysubstituted benzene derivatives using ethyl propiolate with β-dicarbonyl moieties in the presence of DMAP as the catalyst has been reported by Xue et al.. 18
To the best of our knowledge, there is no report of a catalyst-free benzannulation of acetylenic esters with 1,3-dicarbonyl compounds. Based on these findings and as a part of our study on the development of new routes to benzene derivatives, 19 in this paper we report a simple synthesis of functionalized benzene/biaryl and fluoren-9-one systems. Thus, reaction of activated acetylenes with acyclic 1,3-diones and 1,3-indandione in polyethylene glycol (PEG) leads to the corresponding benzene/biaryl and fluoren-9-one derivatives respectively.
RESULTS AND DISCUSSION
The reaction of acyclic 1,3-diones ( 1 ) and activated acetylenes ( 2 ) proceeded smoothly in PEG-400 at 100 ℃ and was complete within 12 h ( 1 ).
Different solvents, such as methanol, ethanol, acetonitrile, tetrahydrofuran (THF) and PEG-400 were explored. The results are summarized in 1 .
As it can be seen from 1 , the best results were obtained by heating the reaction mixture in PEG-400 at 100 ℃ which yielded product 3a in high yield ( 1 , entry 1). Encouraged by this success, we investigated the scope of the reaction of activated acetylenic compounds with acyclic 1,3-diones in PEG-400 at 100 ℃ which led to highly polysubstituted benzene/biaryl systems ( 3a-g ) in 68-87% yields. It was found that high yield was observed when the reaction was stirred at 100 ℃ for 12 h; prolonging the reaction time resulted in no obvious effect on the reaction yield.
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Reaction of acyclic 1,3-diones with activated acetylenes in PEG-400.
Synthetic results of3aunder different reactions conditions
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Synthetic results of 3a under different reactions conditions
The 1 H-NMR and 13 C-NMR spectra of the crude product clearly indicated the formation of tetramethyl 6-benzoylbiphenyl-2,3,4,5-tetracarboxylate ( 3a ) in 87% yield. The reaction was found to be compatible with other acyclic 1,3-diones leading to functionalized benzene/biaryl derivatives in good yields ( 1 ).
The structures of compounds 3a-3g were deduced from their IR, 1 H-NMR and 13 C-NMR spectra. The 1 H-NMR spectrum of 3a exhibited 4 singlets of the H-atoms of the methoxy (3.48, 3.64, 3.92, and 3.93 ppm), alongside characteristic multiplets of the H-atoms of the two phenyl groups. The 1 H-decoupled 13 C-NMR spectrum of 3a showed 23 distinct resonances, which further confirmed the proposed structure. The 1 H-NMR and 13 C-NMR spectra of 3b-3g were similar to those for 3a except for the ester moieties, which exhibited characteristic resonances in the appropriate regions of the spectra.
The reaction of cyclic 1,3-diones such as 1,3-cyclohexanedione, dimedone and 1,3-indandione with activated acetylenic compounds in PEG-400 also was investigated. It was found that the reaction of 1,3-indandione with activated acetylenes proceeds smoothly to produce 9 H -fluoren-9-one derivatives. The reaction was not carried out by the other said cyclic 1,3-diones. Thus the reaction of 1,3-indandione and activated acetylenes in PEG-400 at 100 ℃ led to alkyl 9-oxo-9 H -fluorene-carboxylates ( 4a-d ) in good yields ( 2 ).
The structures of compounds 4a-4d were assigned based on their IR, 1 H NMR and 13 C NMR spectral data. For example, the 1 H NMR spectrum of 4a exhibited four singlets for the methoxy protons at δ = 3.89, 3.91, 4.02 and 4.04 ppm, together with characteristic signals for the aromatic moiety. In the 13 C NMR spectrum, the signals corresponding to the ester carbonyl groups of 4a were observed at δ = 165.0, 165.9, 166.4 and 166.5 ppm. The mass spectrum of 4a displayed the molecular ion peak at m/z = 412. The 1 H and 13 C NMR spectra of 4b-4d were similar to those of 4a except for the alkyl moieties, which exhibited characteristic resonances in appropriate regions of the spectrum. The abovementioned reactions in PEG run in the absence catalyst and products obtained in good yields. It seems the high viscosity of PEG can increase the contact surface between the reagents and generate the adequate position for the reactions to take place.
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Reaction of 1,3-indandione with activated acetylenes in PEG-400 at 100 ℃.
Although the mechanistic details of the formation of compounds 3 and 4 are not known, a plausible rationalization is proposed in 3 . Presumably, the intermediate 7 , which is formed from the successive reaction of dibenzoylmethane and two molecules of DMAD, can undergo enolization and proton transfer reaction to afford the hexatriene 8 . Intermediate 8 can undergo 6π-electrocyclic reaction followed by loss of water to give 3a .
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Proposed mechanism for the formation of compound 3a.
In conclusion, we have revealed an efficient synthesis of functionalized benzene/biaryl and 9 H -fluoren-9-one derivatives from a free catalyzed condensation of activated acetylenes and 1,3-diones in PEG. This frees catalyst process created polysubstituted benzene with some electron-withdrawing groups, which was difficult to construct by other conventional methods. This finding prompted us to explore the feasibility of the construction of polysubstituted benzenes based on utilization of readily available acetylenic esters and 1,3-dicarbonyl moieties. Simple mixing of the starting materials and the potential diversity of this type of reaction are the advantages of this procedure.
EXPERIMENTAL
- General
Acetylenic esters, 1,3-diones and PEG-400 were obtained from Merck and were used without further purification. M.p.: Electrothermal-9100 apparatus. IR spectra (KBr, cm -1 ): Shimadzu IR-460 spectrometer; in cm -1 . 1 H- and 13 C-NMR spectra: Bruker DRX-300 Avance instrument; in CDCl 3 at 500 and 75 MHz, resp.; δ in ppm, J in Hz. MS: Finnigan-MAT-8430 mass spectrometer, at 70 eV; in m/z (rel. %). Elemental analyses (C, H, N): Heraeus CHN-O-Rapid analyzer.
- Typical Procedure for the Preparation of 3(a-g)
To a stirred solution of 1,3-dicarbonyle (2 mmol) was added activated acetylene (4 mmol) in PEG-400 (2 g). The reaction mixture was heated at 100 ℃. After completion of the reaction (12 h), as indicated by TLC (AcOEt/hexane, 2:1), the reaction mixture was cooled to r.t. and the product was extracted with Et 2 O (3 × 4 mL). The solvent was removed under reduced pressure to afford pure 3(a-g) .
- Tetramethyl 6-benzoylbiphenyl-2,3,4,5-tetracarboxylate (3a)
Yield 0.43 g (87%). White crystals, m.p: 123-125 ℃ IR (KBr): [1734, 1726, 1720, 1710, 1682 (C=O)], 1282 (CO). 1 H-NMR: 3.48 (3H, s, MeO), 3.64 (3H, s, MeO), 3.92 (3H, s, MeO), 3.93 (3H, s, MeO), 7.00-7.06 (2H, m, CH), 7.13-7.17 (3H, m, CH), 7.40 (1H, t, 3 J = 7.7 Hz, CH), 7.47 (2H, d, 3 J = 7.6 Hz, CH). 13 C-NMR: 53.0 (MeO), 53.4 (MeO), 53.7 (MeO), 53.8 (MeO), 128.3 (2 CH), 128.6 (2 CH), 128.8 (CH), 129.4 (2 CH), 131.0 (C), 132.1 (2 CH) 133.6 (C), 133.7 (C), 135.4 (C), 137.1 (C), 137.2 (C), 140.9 (C), 141.1 (C), 142.8 (C), 165.9 (COO), 166.0 (COO), 166.8 (COO), 167.1 (COO), 195.5 (C=O). EI-MS: 490 (M + , 6), 459 (4), 258 (18), 167 (55), 149 (100), 105 (42), 77 (28), 59 (15). Anal. calc for C 27 H 22 O 9 (490.45): C 66.12, H 4.52; found: C 66.3, H 4.6.
- Tetraethyl 6-benzoylbiphenyl-2,3,4,5-tetracarboxylate (3b)
Yield 0.46 g (84%). White crystals, m.p: 117-118 ℃. IR (KBr): [1736, 1725, 1721, 1719, 1718 (C=O)], 1257 (C-O). 1 H-NMR: 0.87 (3H, d, 3 J = 7.1 Hz, Me), 0.95 (3H, d, 3 J = 7.1 Hz, Me), 1.31 (3H, d, 3 J = 7.1 Hz, Me), 1.36 (3H, d, 3 J = 7.1 Hz, Me), 3.90 (2H, q, 3 J = 7.1 Hz, CH 2 O), 4.29-4.37 (6H, m, 3 CH 2 O), 6.95-6.99 (2H, m, CH), 7.05-7.10 (3H, m, CH), 7.20 (2H, t, 3 J = 7.7 Hz, CH), 7.37 (1H, t, 3 J = 7.3 Hz, CH) 7.45 (2H, d, 3 J = 7.7 Hz, CH). 13 C-NMR: 13.5 (Me), 13.7 (Me), 14.1 (Me), 14.2 (Me), 62.1 (CH 2 O), 62.2 (CH 2 O), 62.8 (CH 2 O), 62.9 (CH 2 O), 128.2 (2 CH), 128.5 (2 CH), 128.7 (CH), 129.5 (2 CH), 131.7 (C), 132.1 (2 CH), 133.2 (C), 133.6 (CH), 135.6 (C), 136.9 (C), 137.2 (C), 137.3 (C), 140.2 (C), 143.1(C), 165.4 (COO), 165.7 (COO), 166.3 (COO), 166.7 (COO), 195.5 (C=O). EI-MS: 546 (M + , 3), 501 (5), 149 (100), 105 (40), 77 (31), 73 (15). Anal. calc for C 31 H 30 O 9 (546.56): C 68.12, H 5.53; found: C 68.0, H 5.43.
- Dimethyl 6-benzoylbiphenyl-2,4-dicarboxylate (3c)
Yield 0.30 g (81%). White powder. M.p. 123-125 ℃. IR (KBr): [1734, 1724, 1720 (C=O)], 1266 (C-O). 1 H-NMR: 3.36 (3Η, s, MeO), 3.98 (3Η, s, MeO), 7.12-7.17 (4H, m, CH), 7.27-7.32 (3H, m, CH), 7.44 (1H, t, 3 J = 7.6 Hz, CH), 7.54 (2H, t, 3 J = 7.6 Hz, CH), 8.24 (1H, d, 4 J = 1.7 Hz, CH), 8.61 (1H, d, 4 J = 1.7 Hz, CH). 13 C-NMR: 52.7 (MeO), 53.0 (MeO), 128.2 (2 CH), 128.4 (CH), 128.6 (2 CH), 129.2 (2 CH), 129.6 (C), 130.1 (2 CH), 131.4 (CH), 132.2 (CH), 133.4 (C), 133.7 (CH), 137.2 (C), 137.5 (C), 141.9 (C), 144.8 (C), 165.8 (COO), 168.0 (COO), 197.1 (C=O). EIMS: 374 (M + , 4), 341 (6), 151 (100), 105 (41), 77 (34), 59 (15). Anal. calc for C 23 H 18 O 5 (374.39): C 73.79, H 4.85; found: C 73.6, H 4.7.
- Diethyl 6-benzoylbiphenyl-2,4-dicarboxylate (3d)
Yield 0.32 g (79%). White powder. M.p. 110-112 ℃. IR (KBr): [1733, 1728, 1722 (C=O)], 1260 (C-O). 1 H-NMR: 0.82 (3H, d, 3 J = 7.1 Hz, Me), 1.12 (3H, d, 3 J = 7.1 Hz, Me), 3.92 (2Η, q, 3 J = 7.1 Hz, CH 2 O ), 4.08 (2Η, q, 3 J = 7.1 Hz, CH 2 O ), 7.09-7.14 (4H, m, CH), 7.24-7.30 (3H, m, CH), 7.38 (1H, t, 3 J = 7.7 Hz, CH), 7.51 (1H, d, 3 J = 7.7 Hz, CH), 8.15 (1H, d, 4 J = 1.8 Hz, CH), 8.52 (1H, d, 4 J = 1.8 Hz, CH). 13 C-NMR: 13.6 (Me), 13.7 (Me), 62.1 (CH 2 O), 62.6 (CH 2 O), 128.4 (2 CH), 128.5 (CH), 128.7 (2 CH), 129.0 (2 CH), 129.3 (C), 130.6 (CH), 130.7 (2 CH), 131.4 (CH), 132.8 (C), 133.2 (CH), 135.1 (C), 136.6 (C), 139.2 (C), 143.3 (C), 164.9 (COO), 166.3 (COO), 196.2 (C=O). EI-MS: 402 (M + , 6), 347 (5), 151 (100), 105 (52), 77 (40), 73 (45). Anal. calc for C 25 H 22 O 5 (402.44): C 74.61, H 5.51; found: C 74.5, H 5.6.
- Dimethyl 5-acetyl-4-methylisophthalate (3e)
Yield 0.19 g (75%). Yellow oil. IR (KBr): [1726, 1722, 1718 (C=O)], 1260 (C-O). 1 H-NMR: 2.06 (3H, s, Me), 2.60 (3H, s, Me), 3.92 (3H, s, MeO), 3.94 (3H, s, MeO), 8.24 (1H, d, 4 J = 1.6 Hz, CH), 8.47 (1H, d, 4 J = 1.6 Hz, CH). 13 C-NMR: 21.0 (Me), 30.1 (Me), 52.8 (MeO), 53.0 (MeO), 128.0 (C), 131.4 (CH), 133.3 (CH), 133.6 (C), 142.1 (C), 142.9 (C), 165.9 (COO), 167.7 (COO), 202.6 (C=O). EI-MS: 250 (M + , 3), 219 (8), 207 (42), 59 (50), 43 (100). Anal. calc for C 13 H 14 O 5 (250.25): C 62.39, H 5.64; found: C 62.5, H 5.8.
- Tetramethyl 5-acetyl-6-methyl-1,2,34-benzene tetra carboxylate (3f)
Yield 0.25 g (70%). Yellow oil. IR (KBr): [1733, 1730, 1720, 1686, 1680 (C=O)], 1282 (C-O). 1 H-NMR: 2.32 (3H, s, Me) 2.53 (3H, s, COMe), 3.85 (3H, s, MeO), 3.87 (3H, s, MeO), 3.90 (3H, s, MeO), 3.91 (3H, s, MeO). 13 C-NMR: 16.4 (CH 3 ), 31.8 (COCH 3 ), 53.0 (MeO), 53.2 (MeO), 53.4 (MeO), 53.9 (MeO), 129.3 (C), 133.4 (C), 138.0 (C), 140.0 (C), 143.1 (C), 146.2 (C), 165.3 (COO), 165.6 (COO), 166.1 (COO), 167.1 (COO), 203.5 (C=O). Anal. calc for C 17 H 18 O 9 (366.30): C 55.70, H 4.95; found: C 55.67, H 4.96.
- Tetraethyl 5-acetyl-6-methyl-1,2,34-benzene tetra carboxylate (3g)
Yield 0.28 g (68%). Yellow oil. IR (KBr): [1733, 1730, 1720, 1688, 1684 (C=O)], 1280 (C–O). 1 H-NMR: 1.27-1.40 (12H, m, Me) 2.30 (3H, s, Me), 2.52 (3H, s, COMe), 4.28-4.34 (8H, m, OCH 2 ). 13 C-NMR: 13.7 (CH 3 ), 13.8 (CH 3 ), 13.9 (CH 3 ), 14.4 (CH 3 ), 16.4 (CH 3 ), 31.8 (COCH 3 ), 62.1 (OCH 2 ), (MeO), 62.4 (OCH 2 ), (MeO), 62.8 (OCH 2 ), (MeO), 63.2 (OCH 2 ), 128.9 (C), 133.5 (C), 139.0 (C), 142.0 (C), 143.1 (C), 146.5 (C), 165.2 (COO), 165.4 (COO), 166.0 (COO), 167.1 (COO), 203.3 (C=O). Anal. calc for C 21 H 26 O 9 (422.42): C 59.71, H 6.20; found: C 59.68, H 6.18.
- Typical procedure for the preparation of 4(a-d)
To a stirred solution of 1,3-indandione (0.3 g, 2 mmol) was added activated acetylene (4 mmol) in PEG (2 g). The reaction mixture was heated at 100 ℃. After completion of the reaction (12 h), as indicated by TLC (AcOEt/hexane, 2:1), the reaction mixture was cooled to r.t. and the product was extracted with Et 2 O (3 × 4 mL). The solvent was removed under reduced pressure to afford pure 4(a-d) .
- Tetramethyl 9-oxo-9H-fluorene-1,2,3,4-tetracarboxylate (4a)
Yield 0.36 g (88%). Yellow oil. IR (KBr): [1735, 1728, 1723, 1721, 1715 (C=O)], 1256 (C-O). 1 H-NMR: 3.89 (3H, s, MeO), 3.91 (3H, s, MeO), 4.02 (3H, s, MeO), 4.04 (3H, s, MeO), 7.45 (1H, t, 3 J = 7.3 Hz, CH), 7.52-7.64 (2H, m, CH), 7.74 (1H, d, 3 J = 7.4 Hz, CH). 13 C-NMR: 53.6 (MeO), 53.7 (MeO), 53.8 (MeO), 62.0 (MeO), 124.4 (CH), 125.4 (CH), 128.2 (C), 130.0 (C), 131.7 (CH), 132.8 (C) 133.1 (C), 134.6 (C), 136.1 (CH), 138.5 (C), 140.9 (C), 144.4 (C), 165.0 (COO), 165.9 (COO), 166.4 (COO), 166.5 (COO), 189.4 (C=O). EI-MS: 412 (M + , 7), 381 (10), 149 (100), 105 (50), 77 (44), 71 (56), 59 (42). Anal. calc for C 21 H 16 O 9 (412.34): C 61.17, H 3.91; found: C 61.4, H 4.0.
- Tetraethyl 9-oxo-9H-fluorene-1,2,3,4-tetracarboxylate (4b)
Yield 0.40 g (85%). Yellow oil. IR (KBr): [1734, 1727, 1723, 1720, 1719 (C=O)], 1262 (C-O). 1 H-NMR: 0.90 (3H, d, 3 J = 7.1 Hz, Me), 1.02 (3H, d, 3 J = 7.1 Hz, Me), 1.32 (3H, d, 3 J = 7.1 Hz, Me), 1.34 (3H, d, 3 J = 7.1 Hz, Me), 4.12 (2H, q, 3 J = 7.1 Hz, CH 2 O), 4.25-4.32 (4H, m, CH 2 O), 4.36 (2H, q, 3 J = 7.0 Hz, CH 2 O), 7.47 (1H, t, 3 J = 7.6 Hz, CH), 7.53-7.63 (2H, m, CH), 7.70 (1H, d, 3 J = 7.6 Hz, CH). 13 C-NMR: 13.7 (Me), 14.0 (Me), 14.1 (Me), 14.2 (Me), 62.3 (CH 2 O), 62.5 (CH 2 O), 62.8 (CH 2 O), 63.1 (CH 2 O), 124.3 (CH), 125.2 (CH), 128.4 (C), 130.1 (C), 131.8 (CH), 133.0 (C) 133.2 (C), 134.8 (C), 136.3 (CH), 138.6 (C), 140.9 (C), 145.3 (C), 165.1 (COO), 166.0 (COO), 167.5 (COO), 167.9 (COO), 188.8 (C=O). EIMS: 468 (M + , 5), 413 (15), 149 (100), 105 (53), 77 (54), 73 (48), 71 (49). Anal. calc for C 25 H 24 O 9 (468.45): C 64.10, H 5.16; found: C 64.3, H 5.2.
- Dimethyl 9-oxo-9H-fluorene-2,4-dicarboxylate (4c)
Yield 0.25 g (83%). Light brown powder. M.p. 165-167 ℃. IR (KBr): [1734, 1726, 1723 (C=O)], 1264 (C-O). 1 H-NMR: 3.46 (3H, s, MeO), 3.82 (3H, s, MeO), 7.44 (1H, t, 3 J = 7.5 Hz, CH), 7.50-7.61 (2H, m, CH), 7.68 (1H, d, 3 J = 7.5 Hz, CH), 8.30 (1H, d, 4 J = 1.7 Hz, CH), 8.71 (1H, d, 4 J = 1.7 Hz, CH). 13 C-NMR: 51.3 (MeO), 52.5 (MeO), 123.3 (CH), 124.2 (CH), 126.2 (CH), 129.2 (C), 130.9 (CH), 132.1 (CH) 133.6 (C), 135.1 (C), 136.6 (CH), 138.2 (C), 140.3 (C), 145.7 (C), 164.8 (COO), 166.7 (COO), 187.4 (C=O). EI-MS: 296 (M + , 6), 265 (15), 151 (100), 105 (40), 77 (41), 59 (52). Anal. calc for C 17 H 12 O 5 (296.27): C 68.92, H 4.08; found: C 67.9, H 4.1.
- Diethyl 9-oxo-9H-fluorene-2,4-dicarboxylate (4d)
Yield 0.26 g (80%). Light brown powder. Mp: 148-150 ℃. IR (KBr): [1734, 1726, 1724 1613 (C=O)], 1261 (CO). 1 H-NMR: 0.84 (3H, d, 3 J = 7.1 Hz, Me), 1.13 (3H, d, 3 J = 7.1 Hz, Me), 4.06 (2H, q, 3 J = 7.1 Hz, CH 2 O), 4.27 (2H, q, 3 J = 7.1 Hz, CH 2 O), 7.41 (1H, t, 3 J = 7.6 Hz, CH), 7.48-7.57 (2 H, m, CH), 7.61 (1H, d, 3 J = 7.6 Hz, CH), 8.25 (1H, d, 4 J = 1.6 Hz, CH), 8.69 (1H, d, 4 J = 1.6 Hz, CH). 13 C-NMR: 13.3 (Me), 14.3 (Me), 62.8 (CH 2 O), 63.1 (CH 2 O), 124.2 (CH), 125.1 (CH), 125.9 (CH), 127.8 (C), 129.9 (CH), 131.7 (CH) 132.8 (C), 133.6 (C), 135.8 (CH), 137.9 (C), 138.1 (C), 144.1 (C), 164.6 (COO), 165.9 (COO), 190.6 (C=O). EI-MS: 324 (M + , 5), 279 (10), 151 (100), 105 (41), 77 (44), 73 (46). Anal. calc for C 19 H 16 O 5 (324.33): C 70.36, H 4.97; found: C 70.4, H 5.1.
Acknowledgements
We are grateful to Sanandaj Branch, Islamic Azad University Research Council for the financial support of this research.
References
Kaiah T. , Lingaiah B. P. V. , Narsaiah B. , Hireesha B. S. , Kumar B. A. , Gururaj S. , Pathasarathy T. , Sridhar B. 2007 Bioorg. Med. Chem. Lett. 17 3445 -    DOI : 10.1016/j.bmcl.2007.03.087
Kraft A. , Grimsdale A. C. , Holmes A. B. 1998 Angew. Chem., Int. Ed. 37 402 -    DOI : 10.1002/(SICI)1521-3773(19980302)37:4<402::AID-ANIE402>3.0.CO;2-9
Roncali J. 1992 Chem. Rev. 92 711 -    DOI : 10.1021/cr00012a009
Eyley S. C. 1991 In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds. Pergamon New York, U.S.A. Vol. 2 707 -
Snieckus V. 1990 Chem. Rev. 90 879 -    DOI : 10.1021/cr00104a001
Suzuki D. , Urabe H. , Sato F. 2001 J. Am. Chem. Soc. 123 7925 -    DOI : 10.1021/ja0161913
Vollhardt K. P. C. 1977 Acc. Chem. Res. 10 1 -    DOI : 10.1021/ar50109a001
Vollhardt K. P. C. 1984 Angew. Chem., Int. Ed. 23 539 -    DOI : 10.1002/anie.198405393
Bergman R. G. 1973 Acc. Chem. Res. 6 25 -    DOI : 10.1021/ar50061a004
Tierney M. T. , Grinstaff M. W. 2000 J. Org. Chem. 65 5355 -    DOI : 10.1021/jo0055133
Atsumi T. , Murata J. , Kamiyanagi I. , Fujisawa S. , Ueha T. 1998 Arch. Oral Biol. 43 73 -    DOI : 10.1016/S0003-9969(97)00073-3
Koyama H. , Kamikawa T. 1997 Tetrahedron Lett. 38 3973 -    DOI : 10.1016/S0040-4039(97)00793-4
Talapatra S. K. , Bose S. , Mallik A. K. , Talapatra B. 1985 Tetrahedron 41 2765 -    DOI : 10.1016/S0040-4020(01)96378-1
Soehner R. L. , Gambardella M. M. , Hou E. F. , Pollard M. 1974 Proc. Soc. Exp. Biol. Med. 145 1114 -    DOI : 10.3181/00379727-145-37963
Chandra P. , Wright G. 1977 Top. Curr. Chem. 72 125 -
Greenlee M. L. , DiNinno F. , Hammond M. L. 1995 U.S. Patent 5,451,579
Chen J. , Spear S. K. , Huddleston J. G. , Rogers R. D. 2005 Green Chem. 7 64 -    DOI : 10.1039/b413546f
Zhou Q. F. , Yang F. , Guo Q. X. , Xue S. 2007 Synlett. 2073 -
Yavari I. , Moradi L. , Mirzaei A. 2006 Helv. Chim. Acta 89 2918 -    DOI : 10.1002/hlca.200690260