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Synthesis 2011(4): 669-673  
DOI: 10.1055/s-0030-1258416
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Ring-Closing Metathesis Approach to 2H-2-Benzazepine-1,3-diones

Stéphane Lebruna,b, Axel Couture*a,c, Eric Deniaua,b, Pierre Grandclaudona,b
a Université Lille Nord de France, 59000 Lille, France
Fax: +33(3)20436309; e-Mail: axel.couture@univ-lille1.fr;
b USTL, Laboratoire de Chimie Organique Physique, EA CMF 4478, Bâtiment C3(2), 59655 Villeneuve d’Ascq Cedex, France
c CNRS, UMR 8181 ‘UCCS’, Bâtiment C3(2), 59655 Villeneuve d’Ascq Cedex, France

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Publication History

Received 1 December 2010
Publication Date:
19 January 2011 (online)

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Abstract

A series of diversely substituted 2H-2-benzazepine-1,3-diones were efficiently prepared from the unsaturated precursors, N-acyl-o-vinylbenzamides, through a ring-closing metathesis reaction. The parent compounds were easily obtained from the appropriate o-vinylbenzoic acids.

Key words

fused-ring systems - acylation - ring closure - metathesis - imides

Benzo-fused heterocyclic ring systems have received a lot of attention over the years because of their ubiquitous appearance in natural products and modern pharmaceuticals. [¹] 2-Benzazepines and their oxo derivatives at different oxidation levels fall into this category. They are a class of benzo-fused nitrogen-containing seven-membered heterocyclic rings, which are important structural features of marketed drugs, clinical candidates, and other bioactive molecules. [²] As a consequence, the development of synthetic methodologies that may have generality for the construction of multifarious substituted and unsubstituted benzazepines is an area of current interest and alternative methods are currently the object of synthetic endeavor. In this context we envisioned the assembly of the corresponding α,β-unsaturated oxobenzolactams, that is, the 2H-2-benzazepine-1,3-diones 1a-f (Figure  [¹] ). It was anticipated that these highly functionalized models could serve a key role as advanced intermediates prior to the conversion to tailor-made environmentally different benzazepine derivatives as they possess the requisite structure and functional groups location to be easily converted into seven-membered azaheterocyclic models. We surmised that ensuing rather simple chemical manipulation of the latent functionalities would allow for rapid achievement of molecular complexity in a highly efficient manner. Noteworthy compounds of this class are endowed with interesting chemotherapeutic properties. They have indeed been found to be CNS stimulants, in vitro­ antimicrobial agents and to induce motor activity. [³] They are also known to display potent inhibitory activity against cyclic adenosine phosphodiesterase and to act as sunscreen agents. [4] In contrast, the use of benzazepines with an unsaturation in the heterocyclic ring has seen very little synthetic application, [5] probably due to the lack of general synthetic methods for their elaboration. To the best of our knowledge, compounds structurally related to 1a-f have only been obtained by N-alkylation of the corresponding NH-free models derived from PPA-induced annulation of cis-cinnamonitrile-o-carboxylic acid derivatives. [6] The latter compounds have been prepared by inverse­ Beckmann rearrangement of β-nitroso-α-naphthols. [7] This ring-expansion methodology is fraught with difficulties associated with the use of hazardous reagents and its applicability is unsatisfactory mainly because of restrictions in the choice of substituents on the aromatic unit and the seven-membered ring system as well. Additionally the N-phenyl derivative of a bare model has been incidentally obtained through condensation of triphenyl(phenyliminovinylidene)phosphorane with phthal­aldehydic acid. [8]

Figure 1 Targeted 2H-2-benzazepine-1,3-diones 1a-f

Herein we wish to report a conceptually new synthetic approach to a variety of 2H-2-benzazepine-1,3-diones 1a-f based upon the ultimate creation of the alkene moiety embedded in the azaheterocyclic unit on reliance with the ring-closing metathesis (RCM) strategy. Olefin RCM reaction has become a powerful tool in organic synthesis over the past decades, especially when well-characterized ruthenium catalysts were employed. [9] RCM reaction, which ranks high in the hierarchy of synthetic approaches for the elaboration of small, medium, and large unsaturated heterocycles, is now routinely applied to ensure the assembly of cyclic olefins of virtually all ring sizes containing ether, ester, amide, amine, and other functionalities. [¹0] However as far as we know, this annulation technique has not been applied to N-acylamide derivatives.

One way of constructing the targeted compounds 1a-f would be by cyclization of the polyenic diacylamines 2a-f as suitable precursors for the planned RCM reaction. The assembly of these highly functionalized opened models was envisioned and the first facet of the synthesis was the elaboration of the NH-free amides 3a-e, which were readily obtained under standard conditions from the corresponding benzoic acids 4-6 (Scheme  [¹] , Table  [¹] ). Deprotonation of 3a-e with sodium hydride and subsequent interception of the transient sodium amide salt with a suitably (un)substituted acryloyl chloride 7, 8 delivered quite satisfactory yields of the unsaturated N-acyl-o-vinylbenzamides 2a-f (Scheme  [¹] , Table  [¹] ).

Scheme 1 Synthesis of titled 2H-2-benzazepine-1,3-diones 1a-f

Table 1 Compounds 3a-e, 2a-f and 1a-f Prepared
NH-Free o-vinylbenzamide 3
Acryloyl chloride 7, 8
N-Acyl-o-vinylbenzamide
2
2H-2-Benzazepine-1,3-dione
1
R¹ R² R³ Yield (%) R4 Yield (%) Yield (%)
3a H H Me 70 7 H 2a 70 1a 75
3b H H Pr 76 7 H 2b 66 1b 69
3c H H Bn 85 7 H 2c 60 1c 81
3d OMe OMe Me 75 7 H 2d 63 1d 72
3e OCH2O
 Me 82 7 H 2e 65 1e 78
3e OCH2O
 Me - 8 Me 2f 58 1f 70

The targeted imides 1a-f were only one reaction away from the precursors 2a-f. Thus, the ring-closing metathesis experiments was undertaken next and for this purpose the first- and second-generation Grubbs catalysts 9 and 10 were screened (Figure  [²] ). At first, the seven-membered ring precursor 2a underwent ring closure after heating under reflux in CH2Cl2 for 24 hours using 5 mol% first-generation Grubbs catalyst (9; reaction monitored by TLC); however, the benzazepinedione 1a was isolated only in a moderate yield (32%). Increasing the amount of the same catalyst to 10 mol% had no significant impact on the process­ efficiency (35% vs. 32% yield for 1a). However, it was pleasing to observe that the yield could be increased to 75% when the N-acylated o-vinylbenzamide 2a was subjected to 5 mol% of the thermally more stable second-generation Grubbs catalyst (10) under reflux in toluene, which turned out to be the best solvent. These optimal conditions were then used to perform the annulation reaction of the structurally diverse styrene precursors 2b-f. A representative series of compounds, which have been prepared by this technique are presented in Table  [¹] , where it can be seen that this simple procedure affords very satisfactory yields of the targeted 2H-2-benzazepine-1,3-diones 1a-f. The method tolerates the presence of diverse substituents on the aromatic unit and on the diacylated nitrogen atom as well. In strong contrast with the sole reported method for the synthesis of such compounds incorporation of substituents on the alkene moiety could also be envisaged owing to the availability of appropriate acryloyl chlorides, as exemplified by the efficient formation of the substituted model 1f by RCM reaction applied to 2f.

Figure 2 Common ruthenium catalysts used in RCM reactions

In summary, we have devised a short and efficient synthetic strategy towards a variety of hitherto hardly accessible 2H-2-benzazepine-1,3-diones. The key step of the synthetic sequence is based upon the creation of the alkene moiety present in the azepinedione template in the ultimate step via unprecedented RCM reaction.
This technique gives rise to a number of α,β-unsaturated oxolactam-type models, which can be regarded as versatile building blocks with the capacity to incorporate additional substituents/functionalities at a later stage. Applications of this strategy to highly substituted benzazepines synthesis are underway and will be reported in due course.

All solvents were dried and distilled according to standard procedures. Dry glassware was obtained by oven-drying and assembling under dry argon. The glassware was equipped with rubber septa and reagent transfer was performed by syringe techniques. For flash chromatography, Merck silica gel 60 (40-63 µm, 230-400 mesh ASTM) was used. The melting points were obtained on a Reichert-Thermopan apparatus and are not corrected. Elemental analyses were obtained using a Carlo-Erba CHNS-11110 equipment. NMR spectra were recorded on a Bruker AM 300 spectrometer (300 MHz and 75 MHz, for ¹H, and ¹³C) with CDCl3 as solvent and Me4Si as internal standard.

The o-vinylbenzoic acids 4, [¹¹] 5, [¹²] 6 [¹²] were prepared following literature procedures.

4,5-Dimethoxy-2-vinylbenzoic Acid (5)

Mp 183-185 ˚C (Lit. [¹³] mp 183-184 ˚C).

¹H NMR (300 MHz, CDCl3): δ = 3.94 (s, 3 H, OCH3), 3.98 (s, 3 H, OCH3), 5.32 (d, J = 10.9 Hz, 1 Hvinyl), 5.59 (d, J = 17.4 Hz, 1 Hvinyl), 7.05 (s, 1 Harom), 7.57 (s, 1 Harom), 7.64 (dd, J = 10.9, 17.4 Hz, 1 Hvinyl).

¹³C NMR (75 MHz, CDCl3): δ = 56.0 (2 × OCH3), 109.6 (CH2), 113.4 (CH), 115.4 (CH), 119.2 (C), 135.6 (C), 136.2 (CH), 148.0 (C), 152.7 (C), 172.4 (C=O).

6-Vinylbenzo[1,3]dioxole-5-carboxylic Acid (6)

Mp 165-167 ˚C (Lit. [¹²] mp 163-164 ˚C).

¹H NMR (300 MHz, DMSO-d 6): δ = 5.22 (d, J = 11.0 Hz, 1 Hvinyl), 5.65 (d, J = 17.5 Hz, 1 Hvinyl), 6.10 (s, 2 H, OCH2O), 7.20 (s, 1 Harom), 7.28 (s, 1 Harom), 7.46 (dd, J = 11.0, 17.5 Hz, 1 Hvinyl), 12.85 (br s, 1 H, CO2H).

¹³C NMR (75 MHz, DMSO-d 6): δ = 101.9 (OCH2O), 105.8 (CH), 109.3 (CH), 115.2 (CH2), 123.0 (C), 134.5 (C), 134.9 (CH), 146.7 (C), 150.4 (C), 167.6 (C=O).

NH-Free o -Vinybenzamides 3a-e; General Procedure

A mixture of benzoic acid derivative 4-6 (20 mmol), oxalyl chloride (50 mmol), and DMF (0.5 mL) in freshly distilled toluene (40 mL) was stirred for 2 h at r.t.. The solvent was removed under vacuum and the residue was dissolved in CH2Cl2 (10 mL). The solution was added dropwise to a solution of amine R³NH2 (20 mmol) and Et3N (40 mmol) in CH2Cl2 (30 mL) at 0 ˚C, then the mixture was stirred at r.t. for 4 h. H2O (30 mL) was added and the mixture was extracted with CH2Cl2 (2 × 30 mL). The combined organic layers were dried (MgSO4) and the solvent was removed under vacuum. Benzamides 3a-e were purified by flash column chromatography on silica gel using EtOAc-hexanes (80:20) as eluent and finally recrystallized from hexane-toluene (Tables  [¹] and  [²] ).

N -Eneacyl- o -vinylbenzamides 2a-f; General Procedure

A solution of benzamide 3a-e (4.5 mmol) in anhyd THF (5 mL) was added dropwise to a suspension of NaH (5.4 mmol) in anhyd THF (20 mL) at 0 ˚C. The reaction mixture was stirred for 30 min at r.t. and cooled to -78 ˚C. The appropriate acryloyl chloride 7, 8 (9 mmol) was then added dropwise. After stirring for 5 min at -78 ˚C, the mixture was allowed to warm to r.t. over 5 h. H2O (10 mL) was added and the mixture was extracted with CH2Cl2 (2 × 30 mL). The combined extracts were dried (MgSO4) and the solvent was removed under vacuum. The residue was purified by flash column chromatography on silica gel using EtOAc-hexanes (10:90) as eluent to afford N-acylamides 2a-f as yellow oils (Tables  [¹] and  [²] ).

2 H -2-Benzazepine-1,3-diones 1a-f; General Procedure

A solution of N-acylamide 2a-f (1.5 mmol) and second-generation Grubbs catalyst (0.075 mmol, 5 mol%) in anhyd toluene (20 mL) was refluxed under stirring for 5 h under argon (monitored by TLC to establish completion of the reaction). The reaction mixture was concentrated under vacuum and the resulting residue was purified by flash column chromatography on silica gel using EtOAc-hexanes­ (30:70) as eluent to furnish 2H-2-benzazepine-1,3-diones 1a-f as yellow oils (Tables  [¹] and  [²] ).

Table 2 Physical and Spectroscopic Data of Carboxamides 3a-e, N-Eneacylamides 2a-f, and Benzazepinediones 1a-f Prepared (continued)
Producta Mp (˚C) ¹H NMR (CDCl3/TMS) δ, J (Hz) ¹³C NMR (CDCl3/TMS) δ
3a 125-127 (123-124) [¹4] 2.98 (d, J = 5.0 Hz, 3 H, NCH3), 5.34 (dd, J = 1.0, 11.0 Hz, 1 Hvinyl), 5.71 (dd, J = 1.0, 17.5 Hz, 1 Hvinyl), 5.85 (br s, 1 H, NH), 7.02 (dd, J = 11.0, 17.5 Hz, 1 Hvinyl), 7.24-7.31 (m, 1 Harom), 7.35-7.44 (m, 2 Harom), 7.56 (d, J = 7.7 Hz, 1 Harom) 26.8 (NCH3), 116.7 (CH2), 126.2 (CH), 127.4 (CH), 127.7 (CH), 130.1 (CH), 134.5 (CH), 135.7 (C), 150.6 (C), 171.5 (C=O)
3b 62-64
(62-63) [¹4] 		0.97 (t, J = 7.4 Hz, 3 H, CH3), 1.62 (quint, J = 7.4 Hz, 2 H), 3.38 (m, 2 H, NCH2), 5.33 (d, J = 10.9 Hz, 1 Hvinyl), 5.69 (d, J = 17.4 Hz, 1 Hvinyl), 5.98 (br s, 1 H, NH), 7.04 (dd, J = 10.9, 17.5 Hz, 1 Hvinyl), 7.21-7.28 (m, 1 Harom), 7.34-7.45 (m, 2 Harom), 7.56 (d, J = 7.8 Hz, 1 Harom) 11.5 (CH3), 22.8 (CH2), 41.7 (NCH2), 116.6 (CH2), 126.1 (CH), 127.4 (CH), 127.7 (CH), 130.0 (CH), 134.5 (CH), 135.6 (C), 135.7 (C), 169.4 (C=O)
3c 88-90
(88-89) [¹4] 		4.58 (d, J = 5.8 Hz, 2 H, NCH2), 5.12 (d, J = 11.0 Hz, 1 Hvinyl), 5.71 (d, J = 17.5 Hz, 1 Hvinyl), 6.55 (br s, 1 H, NH), 7.06 (dd, J = 11.0, 17.5 Hz, 1 Hvinyl), 7.25-7.53 (m, 8 Harom), 7.82 (d, J = 7.6 Hz, 1 Harom) 43.9 (NCH2), 116.6 (CH2), 126.1 (CH), 127.4 (CH), 127.6 (CH), 128.0 (2 × CH), 128.3 (2 × CH), 130.1 (CH), 131.9 (CH), 134.5 (CH), 135.4 (C), 137.4 (C), 138.3 (C), 169.5 (C=O)
3d 140-142
(colorless crystals) 		2.96 (d, J = 4.8 Hz, 3 H, NCH3), 3.87 (s, 3 H, OCH3), 3.92 (s, 3 H, OCH3), 5.28 (d, J = 10.9 Hz, 1 Hvinyl), 5.59 (d, J = 17.4 Hz, 1 Hvinyl), 6.02 (br s, 1 H, NH), 6.97 (s, 1 Harom), 7.00 (s, 1 Harom), 7.02 (dd, J = 10.9, 17.4 Hz, 1 Hvinyl) 26.8 (NCH3), 55.9 (OCH3), 56.0 (OCH3), 108.5 (CH2), 110.5 (CH), 115.2 (CH), 127.9 (C), 129.0 (C), 134.5 (CH), 140.4 (C), 150.2 (C), 169.6 (C=O)
3e 136-138
(colorless crystals) 		2.93 (d, J = 4.8 Hz, 3 H, NCH3), 5.23 (dd, J = 0.9, 10.9 Hz, 1 Hvinyl), 5.54 (dd, J = 0.9, 17.9 Hz, 1 Hvinyl), 5.92 (s, 2 H, OCH2O), 6.03 (br s, 1 H, NH), 6.86 (s, 1 Harom), 6.89 (dd, J = 10.9, 17.4 Hz, 1 Hvinyl), 6.97 (s, 1 Harom) 26.8 (NCH3), 101.6 (OCH2O), 105.7 (CH), 107.5 (CH), 115.0 (CH2), 129.6 (C), 130.8 (C), 134.1 (CH), 147.1 (C), 149.1 (C), 169.4 (C=O)
2a oil 3.21 (s, 3 H, NCH3), 5.39 (dd, J = 0.9, 11.0 Hz, 1 Hvinyl), 5.56 (dd, J = 1.8, 10.1 Hz, 1 Hvinyl), 5.74 (dd, J = 0.9, 17.3 Hz, 1 Hvinyl), 6.27 (dd, J = 1.8, 16.8 Hz, 1 Hvinyl), 6.46 (dd, J = 10.1, 16.8 Hz, 1 Hvinyl), 6.83 (dd, J = 11.0, 17.3 Hz, 1 Hvinyl), 7.24-7.32 (m, 2 Harom), 7.42-7.49 (m, 1 Harom), 7.58 (d, J = 7.9 Hz, 1 Harom) 32.8 (NCH3), 118.0 (CH2), 126.3 (CH), 127.6 (CH), 128.0 (CH), 128.7 (CH2), 130.6 (CH), 131.0 (CH), 133.1 (CH), 134.9 (C), 135.9 (C), 169.2 (C=O), 172.9 (C=O)
2b oil 0.88 (t, J = 7.4 Hz, 3 H, CH3), 1.64 (quint, J = 7.4 Hz, 2 H), 3.70-3.75 (m, 2 H, NCH2), 5.41 (dd, J = 0.9, 11.0 Hz, 1 Hvinyl), 5.45-5.50 (m, 1 Hvinyl), 5.73 (dd, J = 0.9, 17.4 Hz, 1 Hvinyl), 6.15-6.27 (m, 2 Hvinyl), 6.88 (dd, J = 11.0, 17.4 Hz, 1 Hvinyl), 7.25-7.29 (m, 2 Harom), 7.41-7.47 (m, 1 Harom), 7.59 (d, J = 7.9 Hz, 1 Harom) 11.4 (CH3), 22.1 (CH2), 47.3 (NCH2), 117.8 (CH2), 126.2 (CH), 127.7 (CH), 127.8 (CH), 128.2 (CH2), 130.9 (CH), 131.1 (CH), 133.2 (CH), 135.2 (C), 136.3 (C), 169.2 (C=O), 173.0 (C=O)
2c oil 5.03 (s, 2 H, NCH2), 5.32 (dd, J = 0.9, 10.9 Hz, 1 Hvinyl), 5.45 (dd, J = 5.0, 6.7 Hz, 1 Hvinyl), 5.70 (dd, J = 0.9, 17.4 Hz, 1 Hvinyl), 6.18-6.26 (m, 2 Hvinyl), 6.79 (dd, J = 10.9, 17.4 Hz, 1 Hvinyl), 7.25-7.58 (m, 9 Harom) 48.6 (NCH2), 117.9 (CH2), 126.3 (CH), 127.6 (CH), 127.7 (CH), 128.0 (CH), 128.4 (2 × CH), 128.5 (2 × CH), 128.7 (CH2), 130.7 (CH), 131.3 (CH), 133.1 (CH), 134.9 (C), 136.6 (C), 137.1 (C), 169.3 (C=O), 172.9 (C=O)
2d oil 3.21 (s, 3 H, NCH3), 3.85 (s, 3 H, OCH3), 3.92 (s, 3 H, OCH3), 5.27 (d, J = 10.9 Hz, 1 Hvinyl), 5.48 (dd, J = 1.6, 9.7 Hz, 1 Hvinyl), 5.58 (d, J = 17.2 Hz, 1 Hvinyl), 6.22-6.31 (m, 2 Hvinyl), 6.75 (dd, J = 10.9, 17.2 Hz, 1 Hvinyl), 6.80 (s, 1 Harom), 6.98 (s, 1 Harom) 32.8 (NCH3), 56.0 (OCH3), 56.1 (OCH3), 108.3 (CH), 110.6 (CH), 116.3 (CH2), 127.0 (C), 128.2 (CH2), 130.3 (CH), 130.4 (C), 132.9 (CH), 148.8 (C), 151.3 (C), 169.2 (C=O), 172.8 (C=O)
2e oil 3.23 (s, 3 H, NCH3), 5.29 (d, J = 11.2 Hz, 1 Hvinyl), 5.56 (dd, J = 1.7, 10.1 Hz, 1 Hvinyl), 5.61 (d, J = 17.2 Hz, 1 Hvinyl), 6.05 (s, 2 H, OCH2O), 6.24 (dd, J = 1.9, 16.8 Hz, 1 Hvinyl), 6.42 (dd, J = 10.1, 16.8 Hz, 1 Hvinyl), 6.75 (dd, J = 11.2, 17.2 Hz, 1 Hvinyl), 6.80 (s, 1 Harom), 7.03 (s, 1 Harom) 32.9 (NCH3), 101.9 (OCH2O), 105.9 (CH), 107.7 (CH), 116.6 (CH2), 128.5 (CH2), 128.7 (C), 130.5 (CH), 132.0 (C), 132.7 (CH), 147.5 (C), 150.3 (C), 169.1 (C=O), 172.5 (C=O)
2f oil 1.62 (s, 3 H, CH3), 3.35 (s, 3 H, NCH3), 5.13 (s, 1 Hvinyl), 5.21 (s, 1 Hvinyl), 5.28 (d, J = 10.9 Hz, 1 Hvinyl), 5.57 (d, J = 17.3 Hz, 1 Hvinyl), 6.01 (s, 2 H, OCH2O), 6.67 (s, 1 Harom), 6.76 (dd, J = 10.9, 17.3 Hz, 1 Hvinyl), 7.01 (s, 1 Harom) 18.3 (CH3), 32.8 (NCH3), 101.9 (OCH2O), 105.9 (CH), 108.1 (CH), 116.3 (CH2), 120.7 (CH2), 127.5 (C), 132.5 (C), 133.3 (CH), 142.7 (C), 147.2 (C), 149.8 (C), 172.7 (C=O), 175.3 (C=O)
1a oil 3.51 (s, 3 H, NCH3), 6.47 (d, J = 12.4 Hz, 1 Hvinyl), 7.07 (d, J = 12.4 Hz, 1 Hvinyl), 7.42 (dd, J = 1.6, 7.3 Hz, 1 Harom), 7.55-7.67 (m, 2 Harom), 8.31 (dd, J = 1.7, 7.9 Hz, 1 Harom) 33.3 (NCH3), 125.9 (CH), 130.7 (CH), 131.6 (CH), 132.1 (C), 132.7 (CH), 133.6 (CH), 137.5 (C), 138.3 (CH), 165.8 (C=O), 168.1 (C=O)
1b oil 0.95 (t, J = 7.4, 3 H, CH3), 1.69 (quint, J = 7.4, 2 H), 4.02-4.10 (m, 2 H, NCH2), 6.42 (d, J = 12.4, 1 Hvinyl), 7.02 (d, J = 12.4, 1 Hvinyl), 7.38 (d, J = 7.3, 1 Harom), 7.51-7.62 (m, 2 Harom), 8.23 (d, J = 7.8, 1 Harom) 11.5 (CH3), 21.2 (CH2), 48.1 (NCH2), 126.4 (CH), 130.5 (CH), 131.1 (CH), 132.1 (C), 132.5 (CH), 133.4 (CH), 133.5 (C), 137.7 (CH), 165.6 (C=O), 168.1 (C=O)
1c oil 5.35 (s, 2 H, NCH2), 6.48 (d, J = 12.4 Hz, 1 Hvinyl), 7.06 (d, J = 12.4 Hz, 1 Hvinyl), 7.21-7.33 (m, 3 Harom), 7.38-7.45 (m, 3 Harom), 7.53-7.66 (m, 2 Harom), 8.24 (dd, J = 0.9, 7.6 Hz, 1 Harom) 49.2 (NCH2), 126.2 (CH), 127.3 (CH), 128.3 (2 × CH), 128.4 (2 × CH), 130.7 (CH), 131.4 (CH), 132.2 (C), 132.8 (CH), 133.1 (C), 133.7 (CH), 137.4 (C), 138.2 (CH), 165.7 (C=O), 167.9 (C=O)
1d oil 3.52 (s, 3 H, NCH3), 3.98 (s, 3 H, OCH3), 4.00 (s, 3 H, OCH3), 6.40 (d, J = 12.4 Hz, 1 Hvinyl), 6.81 (s, 1 Harom), 6.97 (d, J = 12.4 Hz, 1 Hvinyl), 7.90 (s, 1 Harom) 33.3 (N CH3), 56.2 (OCH3), 56.3 (OCH3), 113.3 (CH), 115.5 (CH), 124.2 (CH), 126.1 (C), 126.9 (C), 138.1 (CH), 150.6 (C), 152.2 (C), 165.8 (C=O), 166.7 (C=O)
1e oil 3.51 (s, 3 H, NCH3), 6.14 (s, 2 H, OCH2O), 6.40 (d, J = 12.5 Hz, 1 Hvinyl), 6.82 (s, 1 Harom), 6.93 (d, J = 12.5 Hz, 1 Hvinyl), 7.82 (s, 1 Harom) 33.5 (NCH3), 102.7 (OCH2O), 114.4 (CH), 112.9 (CH), 124.3 (CH), 128.8 (C), 130.9 (C), 137.8 (CH), 147.1 (C), 151.2 (C), 165.6 (C=O), 166.8 (C=O)
1f oil 2.25 (s, 3 H, CH3), 3.53 (s, 3 H, NCH3), 6.11 (s, 2 H, OCH2O), 6.75 (s, 1 Harom), 6.96 (s, 1 Hvinyl), 7.69 (s, 1 Harom) 23.3 (CH3), 34.1 (NCH3), 102.4 (OCH2O), 109.6 (CH), 112.0 (CH), 126.5 (C), 128.8 (C), 130.4 (C), 134.7 (CH), 150.5 (C), 152.0 (C), 166.2 (C=O), 168.5 (C=O)
a Satisfactory microanalyses obtained for new compounds: C ± 0.29, H ± 0.26, N ± 0.29.

Acknowledgment

This research was supported by the Centre National de la Recherche Scientifique, by MENESR and by the Program PRIM (Région Nord-Pas de Calais).

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Figure 1 Targeted 2H-2-benzazepine-1,3-diones 1a-f

Scheme 1 Synthesis of titled 2H-2-benzazepine-1,3-diones 1a-f

Figure 2 Common ruthenium catalysts used in RCM reactions