MAGNETIC RESONANCE CHEMISTRYMagnetic Resonance in Chemistry (Magn. reson. Chem.) VOLUME 29 NUMBER 2 FEBRUARY 1991 Contents 2D NOESY Studies on (Pa(y- of the Phenyl and 7-Allyl Moieties H, RUEGGER, R, W, KUNZ, C.J. AMMANN AND F. §. PREGOSIN 191((R)(+)-BINAP}]* Defining the Relative Spatial Orientation Application of 2D EXSY NMR Spectroscopy to the Study of the Dynamic Behaviour of Aroyl- cyanoketene-S,5-dimethylacetals G. FISCHER AND E. KLEINPETER ‘Two-Dimensional NMR Study of Eledoisin TH. YANG, T-Y. CHANG AND C. YU Study of the Distribution of the Electrons in Push-Pull Aikenes by "Hand "C NMR Spectroscopy G. FISCHER, W.D. RUDORF AND E, KLEINPETER Dynamic NMR Study of the Electronic State of Heteroaromatics IX—z-Eleetron Deficiency of ‘Various Substituted Thiazinethiones, Thiazinium Salts and Analogous Pyrimidines by Means of Barriers to Rotation About Exocyclic Partial C,N Double Bonds E. KLEINPETER, W. SCHROTH AND K, PIHLAJA. Isotope Effects on “P Nuclear Shielding in Thiophosphites M. C. DEMARCO, L. LE GLEUT AND B. G. VAN HEMELRYCK, Inverse Edi Spectra U. WOLLBORN AND D, LEIBFRITZ, of Protons in Two-dimensional Homonuclear and Heteronuclear Relayed COSY NMR Spectra and Conformational Analysis of Substituted 2,3-Dihydrof1,S]benzoxazepin-4(SH)-one Derivatives J. OTT, M. HIEGEMANN AND H. DUDDECK "Se, "C and 'H NMR Spectra of Phenylsetenenyleycloalkanes, -cycloalkenes and Some of Their Selenoxides and "Te NMR of a Tellurium Analogue H. DUDDECK, P. WAGNER AND A. BIALLAS Solid-state (CP-MAS) *Si-, '"Sn and Pb Nuclear Magnetic Resonance Study of Bis(penta- methyleyclopentadienyl)-silicon, -tin and -lead B, WRACKMEYER, A. SEBALD AND L. H. MERWIN SC NMR Study of Derivatives of Dibenzobarrelene, Anthraquinone and Anthracene R, SIECKMANN Continued overleaf MRCHEG 29(3) 197-290 (1991) ISSN 0749-1581 7 207 212 23 21 248 260 264MAGNETIC RESONANCE IN CHEMISTRY, VOL. 23, 264-266 (1991) 13C NMR Study of Derivatives of Dibenzobarrelene, Anthraquinone and Anthracene Ralf Sieckmann ‘Ungererst. 19, 8000 Minchen 40, Germany [Carboo-13 chemical shifts of 22 derivatives of dibenzobarrelene, anthraquinone and anthracene are reported, each ‘of which includes a symmetrical ortho-benzene moiety. The assignment of the chemical shifts of the aromatic ‘carbons of these derivatives was achieved by correlation with the corresponding °C chemical shifts of ortho- disubstituted benzenes. KEY worns "°C NMR 23-D-X- 2.5 DiX-anihracenes INTRODUCTION Although there have been several ‘°C NMR investiga- tions dealing with the recording and assignment of para and meta-disubstituted benzene derivatives having two like or two different substituents,} there has hitherto, to my knowledge, been no systematic report on symmetri- cally disubstituted benzene derivatives. The *3C NMR spectra of symmetrically substituted ortho-disubstituted ‘aromatic compounds are only sporadically found in the literature within the series of 1,2-di-X’-benzenes? and 2,3-di-X'-naphthalenes? This work provides, for the first time, "°C NMR chemical shift data for several classes of compounds, namely _2,3-di-X'-carbo- methoxydibenzobarrelenes (I), 2,3-di-X’-9,10-anthra- quinones (2) and 2,3-di-X'-anthracenes (3) (0749-1581/91/030264-03 $05.00 © 1991 by John Wiley & Sons, Ltd. 1,.2-carbomethoxydibenzobarreenes, 2,3-Di-X°S,10-anthraquinones 1 13 Coo Aer bs a) 5 3 RESULTS AND DISCUSSION The chemical shifts of the 2,3-di-X’-dicarbomethoxydi- benzobarrelenes (I) are presented in Table 1. The chemical shifts of the 2,3-di-X'-9,10-anthraguinones (2) are presented in Table 2 together with those of the parent compound anthraquinone, the chemical shifts of which have already been published.* The chemical shifts of the 2,3-di-X’-anthracenes (3) are given in Table 3 together with those of the parent compound anthracene, the chemical shifts of which have already been published. * The assignment of the chemical shifts of the aromatic carbons of the substituted moiety of the compounds mentioned above, and presented in Tables 1-3, was achieved by correlation with the corresponding chemi: cal shifts of the 1,2-di-X’-benzenes. [For correlation the 3 chemical shifts in Ref. 2 (I-VID), supplemented by the measured data of the ultimate paragraph of the present Experimental section, are first normalized to CDCI, 8 = 77.00 (TMS). The correlation coefficient for the compounds 1 always exceeded 0.98, and for com- pounds 2 and 3 they exceeded 0.94.) The °C NMR ‘chemical shifts of 1,2-di-X'-benzenes, which have not been published earlier, i. for X'=CN, CHO and OCOCH,, are presented under Experimental. EXPERIMENTAL The synthesis of the 2,3-di-x”-dicarbomethoxydibenzo- barrelenes (1) has been published elsewhere.® The 2,3-di Received 16 October 1990 Accepted 7 November 19909 NMR STUDY OF DERIVATIVES OF DIBENZOBAI .RRELENE, ANTHRAQUINONE AND ANTHRACENE 265 Table 1. °C NMR chemical shifts (ppm) of dimethyl 2,3-4-X’- 11,12-dicarboxylates (1) C1 12438-11205 10898 118.90 C2 12552 14419 14754 141.03 C5 12438 12348 © 1234312386 C6 1255212532 12521 12559 cs 5238 8182 5230 81.87 Cat 14643 144.56 14840 146.78 G13 14387 14069 14435 13902 C15 14387 13643 19570 143.44 C17 16573 166.48 16598 165.46 C19 5236 5245 52308225 cz 8635 16802 ce 20.38 * Coupling constants (1st order): C-2, F= 260, 6-1, F= },10-etbeno-9,10-dibydroanthracene- . om, coc, ew M1395 125.21 12864 12419 127.69 M4731 1331412801 1296911481 12381 12354 12403 12408 12429 12570 12521 12588 12697 12613, 51655214 5219 614d 14582 147.21 14650 147.16 14549 14301 14414 14262 14241 14200 14015 141.44 14377 140.29 14969 10544 16593 165.39 16528 164.31 5296 5214 8256.52.41 5209 1830 167.60 113.08 2.50 98H, ‘Table 2. 1°C NMR chemical shifts (ppm) of 2,3di-X'-9,10-anthraquinones (2) x Hoek, ocoek, ot coe He 1 12730 108.38 12268 «116.48 12807 12998 12801 127.69, C2 13620 1539014700 18440 14387 13998 13462 144.61 C5 12730 12694 127.91 12743 12694 «12749 «1278412688 €-6 13420 13362 13422 13440 13387 13458 13428 13362 ©9 18320 18232 18140 16092 18302 18124 181.40 18291 G11 19360 13362 13341 13322 13387 13319 19310 19862 C13 13360 12845 13228 13110 131.47 13249 13640 13081 oz 5645 16720 20.00 16640 ©2917 oz 2043 S311 2243, ‘Coupling constants (1st order): C-2, F= 263, C-1, F=17.1, 13, F=3 Hz, ‘Table 3. **C NMR chemical shifts (ppm) of 2,3-di-X'-anthracenes (3) 12810 10499 1204111357 12530 160.23 14112 15026 12810 12766 12798 12853, 42530 12458 12575 127.78 12620 12382 12602 12495 331.70 13082 13184 131.70 191.70 12866 12883 128.40 5581 16841 2059 ‘Coupling constants (1st order): C-2, F= 258, C-1, ‘X’-9,10-anthraquinones (2) and the 2,3-di-X’-anthra- cenes (3) were prepared by generally known methods"? Phthalonitrile and phthaldehyde were purchased from Aldrich Chemical and 1,2-diacetyloxybenzene was Prepared by pyridine-catalysed condensation of cate- chol and acetic anhydride. The '°C NMR spectra were recorded on (A) Bruker 12690 126.8 19530 133.78 12800 12863, 12470 127.76 12470 12950 13130 13088 13130 13203 2040 192.36 F=77,0-13, WH 90 (22.64 MHz), (B) Bruker WH 250 (62.90 MHz) and (©) Bruker WM 400 (100.61 MH2) spectrometers. ‘The pulse width was 6 ps for A, 8 ys for B and 4 ys for Cand FIDs were collected in 8K data points for A, 16K for B and 16K for C with a sweep width of 1000 Fiz for A, 15.625 kHz for B and 25.000 kHz for C. The fip angles were 30°, 30° and 50°, respectively. The number“6 R SIECKMANN of scans ranged from 250 to 20000, depending on solu- bility. The samples were recorded in CDCI, at ambient temperature applying internal deuterium lock, and are referenced to the central peak (5 = 77.00) corresponding to 5 = 0.00 for TMS; the chemical shifts are accurate to at least 0.05 ppm. '°C NMR of 1,2-di-X’-benzenes: 1,2- dicyanobenzene, 115.30 C-1, 13320 C-3, 133.50 C-4, 11388 ppm CN; 1,2-diformylbenzene, 136.38 C-1, 13373 C-3, 13108 'C-4, 192.33 ppm CHO; 1.2 diacetyloxybenzene, 141.90 C-1, 123.10 C-3, 126.10 C-4, 167.60 CO, 20.10 ppm CH. Acknowledgements ‘The author gratefully acknowledges the financial support by the Lehr- stubl fir Organische Chemie 2 of the Rul-Universtat Bochum, and thanks Dr W. Dietrich and co-workers, Lehrstuhl fr Analytische ‘Chemis, Rubr-Universitit Bochum, for recording the NM spectra REFERENCES 1. For 8 review. see H. 0. Kalinowski S. Berger an S. Braun, 1°C- [NMR-Spektroskopie, Kapitel 3, Abschnitt 4.10, pp. 284-314, Thieme Stiga New York’ (1884), and rtsrences ced thaein. 2. Soatr Standard Cordon 13 Catslogue, Heyden, London (1976), No.4), 68 Gi, 181), 240), 1844 0): A ‘Tappley and J. H. Goldstein, J. Phys. Chom. 76, 515 (1872) {Ginter ane Ske Ango. Chm. 86823 (1873) i) 3. G. ikl, W. Hering and H. Gunther, J.Am. Chem. Soe. 96, 323 (1974); J. Seita, T. Drakenberg and J. Sandstrom, Org. Magn ‘Reson. 11, 239 (1876); D. Doddral, M. Barfiald, W. Adcock, M. Aurangzeb and D. Jordan, J. Chem. Soc.. Perkin Trans. 2 402 (1976): N. K. Wilcon and J.B. Stothers J. Magn, Reson. 16.31 (1974): N. K. Wilson and RO. Zeb J. Org. Chom. 43, 1768 (1978); D. Doddrell and P. R. Wells, J. Chom. Soc., Perkin Trans. 21333 (1973); T. Drakenberg, J. Seita and J Sandstrom, Org. Magn. Reson. 11, 246 (1978); P. Granger and M. Maugras, Org. Magn. Reson. 7. 898 (1875): M. Vajda and W Voolter, 2. Naturforch., Tel B 30, 843 (1875). 4.¥, Barger ‘and §" Costonguay, Or. Magn. Reson. 11, 378 (1978), 5. F. Gober, S. Combrisson, N. Platzer and M. Ricard, Org. Magn. ‘Reson. 8, 283 (1976). 6. R.Sieckmann, PRO Thesis, Ruhr-Universitt Bochum (1985). 7. E Joseph and F. Radt (Eds), Elsevier's Encyclopaedia of Organic Chemisty, Serie Ill. Vol.13. pp. 191 ot saq.: Vol. 14, pp. 311 of sag. Elvi, Now York, Amstordam (1946): A. Mal: Foul and ¥: Lepage, Synthesis 689 (1980),