5H-lsoindolo[1,2-b][3]benzazepines IX/ The 1 H and 13 C NMR Spectra of 5H-lsoindolo- [1,2-b][3]benzazepin-5-ones

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1 7. Hyzak, D. L, Diss. Abstr. Int., B 33, 569 (973); Che. Abstr. 80, 88v (974). 8. Jarczyk, H. J., Schriftenr. Ver. Wasser, Boden, Lufthyg., BerlinDahle 972 (37), ; Che. Abstr. 79, 30834y (973). 9. Levenberg, B. and Linton, S. N., J. Bhche. (Tokyo) 24, 846 (966). 0. Dijkstra, J. f Neth. J. Plant Pathol. 75, 32 (969); Che. Abstr. 78, 80885f (973).. Škoda, J., Čihák, A., Gut, J., Prystaé, M., Pískala, A., Párkányi, С, and Šor, F., Collect. Czech. Che. Coun. 27, 736(962). 2. Ross, C, Phytocheistry 3, 603 (964); Che. Abstr. 6, 640e (964).. Taylor, E. С and Martin, S. F., J. Org. Che. 35, 3792 (970). 4. Heinisch, L, Czegowski, W., and Muhlstadt, M., Che. Ber. 97, 5 (964). 5Hlsoindolo[,2b][3]benzazepines IX The H and C NMR Spectra of 5Hlsoindolo [,2b][3]benzazepin5ones S. UHRÍNOVÁ, D. UHRÍN, M. HRICOVÍNI, and B. PROKSA Institute of Cheistry, Slovak Acadey of Sciences, CS Bratislava Received 20 Septeber 99 One and twodiensional NMR ethods were eployed for constitutional studies of 7,8 dihydro5hisoindolo[,2b][3]benzazepin5one derivatives synthesized fro the unnatural alkaloid narceine iide. Their cheical shifts were copared with those of geoetric isoers of substituted benzylideneisoindolin3on.es synthetic precursors of the aboveentioned group of copounds. Chilenine and lennoxaine, plant etabolites with an isoindolo[,2b][3]benzazepine ring syste, isolated fro species of the Berberidaceae faily, constitute a new group of alkaloids []. Several synthetic procedures were developed for their preparation [2 4]; the secophthalideisoquinoline alkaloid narceine iide was the starting aterial for preparation of a series of derivatives and analogues of lennoxaine [5 7]. This paper presents the NMR study of 7,8dihydro5Hisoindolo[,2 b][3]benzazepin5ones, their odel substances and their isoers IV VIII. СНдО^ CH30. ОСОСНз H * For Part VIII see Che. Papers 45, 567 (99). Che. Papers 46 (5) 33^343 (992) 339

2 S. UHRÍNOVÁ, D. UHRÍN, M. HRICOVÍNI, B. PROKSA N OCH, v w Vil Vili H CH 2 CH(OH)CH 3 CH 2 C e H 5 CH 2 COCH 3 OCH, <Z)v<Z)vn The H and H2 protons of all copounds under study appeared in their NMR spectra as AB quartets (Tables 4). The cheical shift of H was deterined unabiguously by the H,HNOESY experient [8] showing its interaction with the H proton; the H2 proton displayed a spatial interaction with protons resonating at 8 = 3.93 ascribed to C3 OCH 3 grouping. The cheical shift of protons belonging to the adjacent ethoxyl group at C4 (5 = 4.) was only sparingly dependent on the structural differences in the reaining part of the olecule of copounds I VIII. A sall upfield ove of the H cheical shift was observed with E isoers ((E)W, ( )W) only. (E)W (E)W Signals of the third ethoxyl group at C2 of the tetracyclic copounds appeared at 5 = 4.0, whilst those of seco derivatives IV VIII were upfield shifted to 5 = for derivatives Z, or to 5 = 3.86 for E ones. An analogous change in cheical shift was also observed with the H proton signal of copounds appearing in the resonance region of aroatic protons (5 = 6.9), but in the spectra of copounds IV VIII these signals were shifted to the polyene region (5 = 6.2) and even to 5 = 5.77 in case of (E)VIII. It could be assued that this change was subject to the twist of coplanarity of the olecule, and consequently, to the change in conjugation of Table. H Cheical Shifts (<5) of Copounds l V Proton II III IV V H 7.53 d 7.54 d 7.50 d 7.44 d.47 d H2 H7 H8 H9 H C4 ОСН3 C2 ОСН3 о COCH dd (5.8;.) 327 dd (5.4; 5.8) 2.88 dd (5.4; 0.4) 6.47 d (0.44) 6.94 s 4. s 5.95 ABq (.5) 2.9 s 7.8 d 7.8 d (6.5) 3.6 dd (4.9; 6.5) 2.99 d (4.9) 6.36 s 6.97 s 5.95 ABq (.5).85 s 7.2 d s 6.83 s 4.08 s 5.95 s 7.5 d s 624 s 4.2 s 5.98 s 224 s 7.7 d 5.60 dd (7.4;.) 5.8 dd (0.9;.) 6.74 dd (0.9; 7.4) 6.8 s 6.30 s 3.96 s 5.95 s 340 Che. Papers 46 (5) (992)

3 5HISOINDOLO[ t2b][3)benzazepines. IX Table 2. Carbon C Cheical Shifts (dj of Copounds I V C 4.7 C2 72 C C4 C4a 9.3 C C7 70. C C8a.5 C C C 5. C C2a 20.8 C 99.4 Ca 2. Cb C4 OCH3 C2 OCH, j 59.8 о COCH 3 II III IV V double bonds, which is higher with cyclic structures of than with seco derivatives IV VIII. The H proton in copound is located in the plane of the benzene ring D and shielded by this ring and therefore, its signal was observed ore downfield. On the other hand, the benzene ring D in copound IV is partly deviated fro the plane intersecting rings А, В and the C Ca double bond due to a rotation around the C2a C bond; as a result, the proton H appeared in the shielding sphere of ^electrons of the benzene ring D. The change in the cheical shift of signal belonging to C2 OCH3 can be rationalized in the sae way; nevertheless, here the shielding was caused by the ring A and possibly by the double bond in conjugation with it. Change in the planarity of olecules of vs. IV, V was observed in the C NMR spectra in the shift of C2a and C signals and in the UV spectra of copounds by bathochroic and hyperchroic shifts. Conforation of the dihydroazepine ring of copounds was ainly deduced fro the H NMR spectra. Spatial interaction recognized fro the NOE difference spectru evidenced the N(CH 3 )2 and CH3CO groups in and, respectively, interacting with protons H, H2, H and C2 OCH3, to be axially bonded. The coupling constant values 3 J H, H indicated that the equatorially bonded proton H7 disclosed a spinspin interaction with the proton H8eq only and consequently, they occupied a synperiplanar orientation. Signal of the H8eq proton is ore downfield shifted than the axially oriented counterpart as a result of a deshielding effect of the benzene ring D. This arrangeent of copound was backed by the appearance of an interaction between H8ax and H9 ( 4 J H, H) Absence of the substituent at C7 in Table 3. H Cheical Shifts (5) of Copounds W VIII Hydrogen (Z)W (E)Vŕ (Z)wr (EyVIII H H2 H7a H7b H8 H9 H C4 OCH3 C2 OCH3 о CH 2 CH CH(OH) CH 3 с в н d 5.59 dd; 5.58 dd 5.6 dd 6.68 dd; 6.64 dd 6.84 s; 6.82 s 6.29 s; 627 s 4.0 s 3.98 s 5.98 s*; 5.96 ABq* 0.80 d; 0.82 d (6.; 5.8) 6.86 d 6.34 d 5.32 dd (7.5;.0) 4.86 dd; 4.85 dd 6.7 dd 6.89 s; 6.88 s 6.5 s; 6. s 3.83 s 4.05 s 3.87 s 6.0 ABq 28 d; 27 d (6.3) 7.45 d; 7.47 d 5.53 dd; 5.60 dd 5.08 dd; 524 dd 6.5 dd; 6.72 dd 6.77 s; 6.82 d 62 s; 6.30 s 3.54 s; * 4.5 s; 4. s 3.94 s; 3.96 s* 5.92 ABq; 5.97 s 5.04 d; 4.49 d (62) 7.07 ; d (8.5) 6.60 d (8.5) 5.53 dd 5.05 dd 6.69 dd 6.87 s 5.77 s 3.83 s* 4.07 s 3.86 s* 5.99 ABq s e) Two distinct Z and E isoers were present in solution of which only soe proton signals were resolved and appeared as two bands; * abiguously assigned; ultiplet in a broad range (8 = ). Che. Papers 46 (5) (992) 34

4 S. UHRÍNOVÁ, D. UHRÍN, M. HRICOVÍNI, B. PROKSA Table 4. C Cheical Shifts (dj of Copounds VI Vlil Carbon C C2 C3 C4 C4a C5 C7 C8 C8a C9 C0 C C2 C2a C Ca Cb C4 OCH3 C2 OCH3 осн2о CH 2 CH(OH) CH 3 c=o свн5 (E)Vr (Z)wr (E)VIII ; ; ; ; 68.3; 22.0; ; 4.0; 4.7; ; 49.4; ; ; 26.2; * * ; 27.8 a) Cheical shifts of preferred isoers only; soe carbons afforded two spectral bands. Minor constituents (Z)W and (E)VII are also in solution; *abiguously assigned. the olecule of copound conditioned a greater conforational freedo of the С ring between C7 and C8 visualized by the unresolved ultiplets of hydrogen signals and the equilibrated value of the dioxyethylene grouping signals appearing as a siple singlet. Signals of this grouping in ore or less rigid structures of and occurred as a sharp AB quartet. Opening of the С ring and introduction of a further substituent at the iino nitrogen favoured a greater flexibility of the C2a C bond and, e.g. another Z to E ratio of isoers of copound VI. This effect was also observed with analogous copounds substituted at the iide nitrogen [7]. Copound VI, affording Z and E isoers showed, after equilibration, a preferential foration of the E isoer with a great twist of the benzylidene oiety fro coplanarity, this being particularly anifested by shielding the H and H2 hydrogens by nelectrons of this ring and by a considerable upfield shift when copared with that of the Z isoer. The sae effect was also encountered with signals of H7 and H protons; on the other hand, the H8 proton and the CH 3 group protons of the substituent were partly deshielded and observed ore downfield (Table 3). Replaceent of hydrogen for a 2hydroxypropyl group on the iide nitrogen of copound V was associated with origination of 342 a chiral centre in the benzylideneisoindolin3one oiety. The NMR spectra of copound VI evi denced the existence of four (two Z and E each) isoers in solution, both being seen in duplication of proton signals bonded in the proxiity of the chiral centre. This effect was rearkable with H9, H, H7, H8 and in saller extent also with the H2 proton signals in addition to those belonging to the 2hydroxypropyl group. The E isoer having the H7, H8, and H9 protons ore reote fro the chiral centre displayed, in coparison with the Z one, a shorter distance between the correspond ing bands. The existence of four various isoers in solution was proved by the DNOE difference easureents [9, 0] as well. A siilar behaviour revealed also copound VII bearing the CH 2 C 6 H 5 substituent, which equilibrated to give a greater aount of isoers seen as several series of spectral bands around the region of substituent resonance. This phenoenon prevented a ore principal analysis of the spectru. The H NMR spectru of copounds VI and VII contained signals of the dioxyethylene group as both singlet and AB quartet. Foration of a series of bands of the particular isoers was also observed in the C NMR spectru, but the cheical shift changes of spectral lines were less significant and therefore, Table 4 lists cheical shifts of the preferred isoer only. The ketone VIII, obtained by oxidation of co pound VI, is therodynaically stable as an E isoer (proved by the H NMR data (Table 3) and NOE experients) characteristic of an upfield shift of H, H2, and H proton signals. The NOE difference spectru showed a spatial interaction of H and H7 protons with H8 and H9, respec tively, and concurrently an interaction of the CH 2 group protons of the substituent with H. EXPERIMENTAL The H and C NMR spectra of deuterochlorofor solutions of copounds containing tetraethylsilane as an internal reference were recorded at 25 C with a spectroeter AM300 (Bruker) operating at 300 and 75 MHz for H and C nuclei, respectively. Signals of the NMR spectra (Tables 4) were ascribed according to H,HCOSY experients [] (for H nuclei), the protonated carbons were identified fro either undecoupled C or H,CCOSY [2] spectra, quaternary carbons fro the seiselective INEPT experient [] optiized for the longrange interactions. The dipóle dipóle interactions were investigated eploying the DNOE [9, 0] or 2DNOESY [8] experients. Che. Papers 46 (5) (992)

5 REFERENCES. Valencia, E. f Weiss, I., Firdous, S., Freyer, A. J., Shaa, M., Urzua, A., and Fajardo, V., Tetrahedron 40, 3957 (984). 2. Moody, Ch. and Warrellow, G. J., Tetrahedron Lett. 28, 6089 (987). 3. Mazzocchi, P. H., King, С R., and Aon, H. L, Tetrahedron Lett. 28, 2473 (987). 4. Fang, F. G. and Danishefsky, S. J., Tetrahedron Lett. 30, 2747.(989). 5. Proksa, В., Uhrín, D., and Vadkerti, A., Che. Papers 42, 683 (988). 6. Proksa, В., Fuska, J., and Votický, Z., Pharazie 37, 350 (982). 7. Proksa, В., Vadkerti, A., and Uhrín, D., Che. Papers 45, 95 (99). 8. Jeener, J., Meier, B. H. ( Bachann, P., and Ernst, R. R., J. Che. Phys. 7, 4546 (979). 9. Neuhaus, D., J. Magn. Reson. 53, 09 (983). 0. Kinns, M. and Sanders, J. K. M. f J. Magn. Reson. 56, 58 (984).. Aue, W. P., BarthokJi, E., and Ernst, E. E., J. Che. Phys. 64, 2229 (976). 2. Bax, A., J. Magn. Reson. 53, 57 (983).. Bax, A., J. Magn. Reson. 57, 34 (984). Translated by Z. Votický Photooxidation of Hydroxyethylcellulose Changes in Physical Properties due to Corona Discharge a J. POLAVKA and b L LAPČÍK ^Departent of Physical Cheistry, Faculty of Cheical Technology, Slovak Technical University, CS82 37 Bratislava departent of Printing Art and Applied Photocheistry, Faculty of Cheical Technology, Slovak Technical University, CS82 37 Bratislava Received 29 October 99 The photooxidation of hydroxyethylcellulose by the action of corona discharge in air was studied at 25 C. The influence of exposure on physical properties of polyer fil was exained. It has been found that the transport process of diffusion of the distilled water into the polyer obeys the second Fick's law in the first period of one. The easured average apparent diffusion coefficient of the studied syste varies in the interval (2. 5.2) x 0" 0 2 s~ and decreases with exposure in an equal anner as the activation energies of diffusion which vary in the interval ( ) kj oľ. On the basis of liiting contact angle easureents the teperature of glass transition was deterined. It has been found that the preponderance of the crosslinking process over photodestruction of the polyer is significantly influenced by the tie of irradiation by lowteperature plasa of corona source. The photodegradation of cellulose aterials has been extensively investigated [ 5]. The priary process is chain scission which occurs during UV irradiation (at A = n) of cellulose yielding any different copounds, e.g. xylose, Dglucose, and cellobiose. Many volatile products such as acetaldehyde, acetone, ethanol, ethanol, ethane, water vapour are fored. These copounds are the results of the secondary degradation process, ľhe coposition of the photodegradation products depends on the syste used. The following echanis for the priary process has been proposed (Schee ). Foration of free radicals during irradiation of cellulose with light has been verified by EPR spectroscopy [,2]. As obvious, the study of both kinetics and the echanis of photocheical reactions in polyer aterials has lately ade a great progress and is very iportant fro the viewpoint of polyer application. The lowteperature plasa treatent of polyer surface has been recently studied because of the ability to odify a polyer surface without great affecting its bulk properties. It can be presued that the high speed of plasocheical surface reactions results fro the plasa effectiveness solid surface energy transfer by electrons, excited atos and ions collisions. During the past few years there has been a steady growth in the use of plasa for the odification of the surface properties of various solid aterials [6 9]. This interest has been otivated by the ability Zhe. Papers 46 (5) (992) 343