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Reaction of N1,N2-Diarylacetamidines with2,3-Dicyano-1,4-naphthoquinone†
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Reaction of N1,N2-Diarylacetamidines with2,3-Dicyano-1,4-naphthoquinone†
作者:
Mohsen A. Gomaa,
期刊:
Journal of Chemical Research, Synopses
(RSC Available online 1997)
卷期:
Volume 0,
issue 8
页码: 284-285
ISSN:0308-2342
年代: 1997
DOI:10.1039/a700766c
出版商: RSC
数据来源: RSC
摘要:
Me NAr NHAr + CN CN O O O O CN NAr Me NAr NH 1a–d 2 3a–d NAr NAr OH O CN NH NAr NHAr O– O CN NH O O CN 4a–d NAr NH NHAr + 5a–d O O CN CN 7 6a–d a Ar = Ph b Ar = 4-MeC6H4 c Ar = 4-MeOC6H4 d Ar = 4-ClC6H4 284 J. CHEM. RESEARCH (S), 1997 J. Chem. Research (S), 1997, 284–285† Reaction of N1,N2-Diarylacetamidines with 2,3-Dicyano- 1,4-naphthoquinone† Mohsen A. Gomaa,* Shaaban K. Mohamed and Ahmed M. Nour El-Din Chemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Arab Republic of Egypt The reaction of the N1,N2-diarylacetamidines 1a–d with 2,3-dicyano-1,4-naphthoquinone (2) led to the formation of benzo[f ]isoquinoline derivatives 6a–d; the reaction mechanism is discussed. One of the two cyano groups of 2,3-dicyano-1,4-naphthoquinone 2 undergoes substitution with primary amines, while the second cyano group is inert towards nucleophilic substitution. 1 Arylaminopyrazoles react with the nitrile 2 by replacement of one of the cyano groups followed by the addition (by their amino group) on the second cyano group to give pyrazolo[2,3-a]quinazolinediones.2 From the reaction of 2 with N,N-diarylbenzylideneanilines, 2-arylamino-3-cyano- 1,4-naphthoquinone together with the corresponding aldehydes are obtained, probably due to the hydrolysis of the primary substitution products.3 In an earlier publication4 we reported that the reaction of 2-(1,3-dioxo-2,3-dihydro-1Hinden- 2-ylidene)malononitrile 7 with N,Np-diarylacetamidines affords the corresponding indeno[1,2-d]azepines.However it has been reported that 7 undergoes a fast rearrangement with electron donors like acetamidines into 2,3-dicyano-1,4-naphthoquinone (2).5 Here we present the results obtained with the reaction of the diarylacetamidines 1a–d with 2. These results are compared with those obtained with the isomer of 2, i.e. 7. N1,N2-Diarylacetamidines 1a–c reacted with 2 in ethyl acetate at room temperature to give the benzo[ f ]isoquinolines 6a–d (in 40–72% yield).The IR spectra of 6a–d showed characteristic absorptions at vmax 3307–3340 cmµ1 for the hydroxy groups and at 3240–3250 cmµ1 for the NH group with further bands at 2190–2195 cmµ1 for the CN group and at 1681–1682 cmµ1 for the CO group. 1H NMR AB patterns with dA 2.99–3.02 and dB at 3.31–3.36 with |2J|-values 17.02–17.31 Hz are assigned to the C-1 methylene group adjacent to the chiral carbon atom C-10b. The presence of this methylene group is also evident from the 13C-DEPT spectra which exhibit negative signals at d 38.63–38.87. The broad band 1H-decoupled 13C NMR spectra showed one signal each at d 79.30–82.5 for C-10b bearing the hydroxy group and one signal each at d 117.71–119.50 for the cyano group.It is interesting to mention that the position of the signals of the olefinic C-atoms bearing the cyano groups, i.e. C-5 in 6a–d, show up at relatively higher field at d 57.06–57.20. The unexpected upfield shift in the range d 57–60 for the sp2 carbon attached to the nitrile group has been previously reported.6,7 It is plausible that the origin of the methylene group is the acetyl-derived methyl group in the acetamidines 1a–d.The formation of the benzo [ f ]isoquinolines 6a–d can be rationalized as follows: initial nucleophilic attack by the N2 of 1a–d on one nitrile carbon of 2 gives rise to compounds 3a–d which are in equilibrium with the tautomers 4a–d.8,9 The latter, being essentially ketene aminals, exhibit nucleophilic character at the terminal methylene carbon atom which attacks C-1 of 2 giving 5a–d which are ultimately isolated as 6a–d.From the above findings it may be concluded that the reaction of 7 with the acetamidines 1a–d is faster than the isomerization to 2. This may be ascribed to the fact that the basicity of the acetamidines 1a–d is not big enough to catalyse such a rearrangement. Experimental Melting points are uncorrected and obtained using a Griffin Georg melting point apparatus. Elemental analyses were obtained using a Carlo Erba 1106 CHN-analyser. Ir spectra were run as potassium bromide discs using a Shimadzu 470 spectrometer. 1H and 13C NMR were run at 300 and 75 MHz respectively using a Bruker WM 300 spectrometer with TMS as internal standard, m=multiplet.Mass spectra were run at 70 eV electron impact mode using a MAT 311A in connection with an AMD DP-10 data processing system. For preparative layer chromatography (PLC), an air dried 1.0 mm thick layer of slurry applied silica gel Merck PF254 on 48 cm wide and 20 cm high glass plates was employed using the solvents listed.Zones were detected by quenching of indicator fluorescence upon exposure to 254 nm light and eluted with acetone or ethyl acetate. The starting materials 2,3-dicyano-1,4-naphthoquinone10 (2) and N,Np-diarylacetamidines11 1a–d were prepared according to literature procedures. General Procedure for the Reaction of N,Np-Diarylacetamidines 1a–d with 2,3-Dicyano-1,4-naphthoquinone (2).·A solution of 2 (208 mg, 1.0 mmol) in 10 ml ethyl acetate was added dropwise to a solution of acetamidine (1a–d, 1.0 mmol) in 10 ml ethyl acetate at room temperature. After 10 min yellow crystals of benzo[ f ]isoquinolines 6a–d precipitated which were filtered off and recrystallized from ethyl acetate.The filtrate was evaporated and the residue was subjected to PLC using toluene–ethyl acetate (2:1) as eluent to give one zone which contained compounds 6a–d.*To receive any correspondence. †This is a Short Paper as defined in the Instructions for Authors, Section 5.0 [see J. Chem. Research (S), 1997, Issue 1]; there is therefore no corresponding material in J. Chem. Research (M).J. CHEM. RESEARCH (S), 1997 285 1 0 b - H y d r o x y - 4 - i m i n o - 3 - p h e n y l - 2 - p h e n y l i m i n o - 6 - o x o- 1 , 2 , 3 , 4 , 6 , 1 0 b - hexahydrobenzo[f]isoquinoline-5-carbonitrile (6a).·Yellow crystals (300 mg, 72%) mp 210–211 °C (from ethyl acetate), vmax (KBr)/ cmµ1 3321 (OH), 3240 (NH), 2184 (CN), 1682 (CO); dH (300 MHz, [2H6]DMSO) 2.99 (1 H, d, 1ap-H), 3.35 (1 H, d, 1bp-H, |2J| 17.15 Hz, CH2), 6.87, 7.02, 7.30, 7.39, 7.81, 7.83 and 7.97 (14 H, all m, aryl-H) and 7.50 (2 H, br, NH and OH); dC (75 MHz, [2H6]DMSO) 38.87 (C-1), 57.09 (C-5), 82.50 (C-10b), 118.50 (CN), 120.81, 120.59, 125.26, 127.18, 128.32, 128.98, 129.76 and 135.39 (all aryl- CH), 131.24 and 134.06 (C-6a and C-10a), 135.75 (C-4a), 148.61 (two aryl-C-N), 158.34 (C-2), 163.50 (C-4) and 193 (C-6); m/z 418 (M+, 6%), 391 (15), 247 (75), 210 (28), 170 (16), 155 (31), 118 (100), 93 (50), 77 (97) (Found: C, 74.52; H, 4.41; H, 13.20.C26H18N4O2 requires C, 74.62; H, 4.34; N, 13.39%). 1 0 b - Hydroxy- 4 - imino- 3 - (4 - methylphenyl) - 2 - (4 - methylphenylimino) - 6 - oxo- 1,2,3,4,6,10b - hexahydrobenzo[f]isoquinoline- 5 - carbonitrile (6b).·Yellow crystals (178 mg, 40%) mp 172–173 °C (from ethyl acetate); vmax (KBr)/cmµ1 3314 (OH), 3240 (NH), 2192 (CN), 1682 (CO); dH (300 MHz, [2H6]DMSO) 2.23 (3 H, s, CH3), 2.39 (3 H, s, CH3), 2.99 (1 H, d, 1ap-H), 3.33 (1 H, d, 1bp-H |2J| 17.31 Hz, CH2), 4.03 (2 H, br, NH and OH) and 6.75, 7.09, 7.25, 7.38, 7.63, 7.82 and 7.94 (12 H, all m, aryl-H); dC (75 MHz, [2H6]DMSO) 20.54 and 20.96 (two CH3), 38.86 (C-1), 57.20 (C-5), 80.50 (C-10b), 119.50 (CN), 122.73, 127.07, 128.05, 129.71, 130.40 and 135.59 (all aryl-CH), 125.31 and 131.19 (C-6a and C-10a), 132.59 (C-4a), 138.79 (two aryl-C-CH3), 145.88 (two aryl-C-N), 158.27 (C-2), 163.50 (C-4) and 193.01 (C-6); m/z 466 (M+, 4%), 419 (34), 404 (10), 390 (4), 329 (17), 278 (15), 261 (15), 171 (10), 106 (100), 91 (22), 77 (19) (Found: C, 75.45; H, 5.12; N, 12.32.C28H22N4O2 requires C, 75.32; H, 4.97; N, 12.55%). 10b - Hydroxy- 4 - imino- 3 - (4 - methoxyphenyl) - 2 - (4 - methoxyphenylimino- 6 - oxo- 1,2,3,4,6,10b - hexahydrobenzo[f]isoquinoline- 5 - carbonitrile (6c).·Yellow crystals (200 mg, 42%) mp 159 °C (from ethyl acetate); vmax (KBr)/cmµ1 3340 (OH), 3240 (NH), 2187 (CN), 1682 (CO); dH (300 MHz, [2H6]DMSO) 3.02 (1 H, d, 1ap-H), 3.36 (1 H, d, 1bp-H, |2J| 17.23 Hz, CH2), 3.69 (3 H, s, OCH3), 3.82 (3 H, s, OCH3), 6.84, 7.13, 7.36, 7.63, 7.82 and 7.95 (12 H, all m, aryl-H) and 6.88 (2 H, br, NH and OH); dC (75 MHz, [2H6]DMSO) 38.63 (C-1), 55.08 and 55.39 (two OCH3), 57.06 (C-5), 79.30 (C-10b), 114.24, 114.98, 121.78, 125.10, 126.71, 129.25, 130.53 and 135.31 (all aryl-CH), 119.5 (CN), 125.78 and 127.28 (C-10a and C-6a), 136.80 (C-4a), 140.97 (two aryl-CN), 155.70 and 159.50 (two aryl- C-OCH3), 159.50 (C-2), 163.90 (C-4) and 193.08 (C-6); m/z 478 (M+, 5), 451 (26), 436 (34), 420 (5), 419 (13), 345 (13), 294 (81), 149 (7), 123 (83), 108 (100), 92 (5), 77 (11) and 65 (6) (Found: C, 69.98; H, 4.70; N, 11.60.C28H22N4O4 requires C, 70.28; H, 4.62; N, 11.71%). 10b - Hydroxy - 4 - imino - 3 - (4 - chlorophenyl) - 2 - (4 - chlorophenylimino) - 6 - oxo- 1,2,3,4,6,10b- hexahydrobenzo[f]isoquinoline- 5 - carbonitrile (6d).·Yellow crystals (314 mg, 65%) mp 175–178 °C (from ethyl acetate); vmax (KBr)/cmµ1 3307 (OH), 3250 (NH), 2192 (CN), 1681 (CO); dH (300 MHz, [2H6]DMSO) 3.01 (1 H, d, 1ap-H), 3.31 (1 H, d, 1bp-H, |2J| 17.02 Hz, CH2), 6.92, 7.32, 7.40, 7.61, 7.86 and 7.98 (12 H, all m, aryl-H), and 7.67 (2 H, br, NH and OH); dC (75 MHz, [2H6]DMSO) 38.86 (C-1), 57.15 (C-5), 84 (C-10b), 118.55 (CN), 122.51 (C-10a), 122.83, 125.24, 127.29, 129.09, 129.62, 130.24, 132 and 135.65 (all aryl-CH), 127.63 (C-6a), 133.13 and 133.34 (aryl-C-Cl), 135.65 (C-4a), 147.68 (two aryl-C-N), 158.93 (C-2), 162.50 (C-4) and 192.84 (C-6); m/z 487 (M+, 18), 348 (7), 298 (14), 152 (23), 127 (100), 92 (18), 76 (10) and 65 (22) (Found: C, 64.12; H, 3.20; N, 11.42.C26H16Cl2N4O2 requires C, 64.06; H, 3.31; N, 11.50%). We are indebted to Prof. Dr Dietrich D�opp, Division of Organic Chemistry, Gerhard Mercator Universit�at GH Duisburg, for measuring the elemental analyses, 1H NMR and mass spectra. Received, 3rd February 1997; Accepted, 18th April 1997 Paper E/7/00766C References 1 K.-Z. Chu and J. Griffins, J. Chem. Soc., Perkin Trans. 1, 1978, 1083. 2 A. A. Hassan, N. K. Mohamed, Y. R. Ibrahim and A. E. Mourad, Liebigs Ann. Chem., 1993, 695. 3 M. A. Gomaa, Bull. Chem. Soc. Jpn., 1995, 68, 3131. 4 D. D�opp, M. A. Gomaa, G. Henkel and A. M. Nour El-Din, J. Chem. Soc., Perkin Trans. 2, 1996, 573. 5 G. J. Ashwell, M. R. Bryce, S. R. Davies and M. Hassan, J. Org. Chem., 1988, 53, 4585. 6 R. Dworczk, H. Sterk, C. Kratky and H. Junek, Chem. Ber., 1989, 122, 1323. 7 W. Bremser, B. Frank and H. Wagner, Chemical Shift Ranges in NMR Spectroscopy, Verlag Chemie, Weinheim, 1982. 8 H. P. Figeys, A. Mathy and A. Dralants, Synth. Commun., 1981, 11, 655. 9 M. Pfau, M. Chiriacescu and G. Revial, Tetrahedron Lett., 1993, 34, 327. 10 G. A. Renolds and J. A. Vanallan, J. Org. Chem., 1964, 29, 3591. 11 E. C. Taylor and W. A. Erhart, J. Org. Chem., 1963, 28,
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