In order to achieve full conversion, the temperature had to be raised to 50 °C, upon which the aromatic ring of part of the starting material was hydrogenated to furnish the N‐(cyclohexylmethyl) congener 18 h (10 %). 13C{1H} NMR (125 MHz, CDCl3), major isomer: δ=23.65 (CH2), 32.72 (CH2), 36.43 (CH2), 50.51 (CH), 52.06 (CH3), 52.40 (CH2), 125.25 (CH), 126.15 (CH), 127.27 (CH), 127.67 (CH), 128.37 (2 CH), 128.86 (CH), 128.88 (2 CH), 137.53 (C), 139.87 (C), 141.94 (C), 155.78 (C), 174.04 (C) ppm; minor isomer: δ=20.80 (CH2), 31.98 (CH2), 32.16 (CH2), 51.97 (CH3), 52.43 (CH2), 54.86 (CH), 127.32 (CH), 127.87 (CH), 128.33 (CH), 128.57 (CH), 128.68 (2 CH), 129.17 (2 CH), 131.75 (CH), 137.22 (C), 138.94 (C), 140.47 (C), 155.79 (C), 173.43 (C) ppm. We are furthermore grateful to Dr. R. Kadyrov (Evonik, Hanau) for providing us with a sample of ruthenium catalyst. The combined organic layers were dried (MgSO4), filtered and the solvent was removed in vacuo. Ester saponification and amide coupling. Long Zhang, Jilin Provincial Engineering Laboratory for the Complex Utilization of Petro‐resources and Biomass, School of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China. The authors declare no conflict of interest. via The N‐unsubstituted parent amide 27 d was obtained by amidation with (NH4)2CO3 and could be further transformed by Hofmann degradation using PhI(OAc)2 (PIDA) and MeOH to give carbamate 28 (30 % yield). 1H NMR (500 MHz, CDCl3): δ=1.14 (s, 3 H), 1.19 (t, J=7.1 Hz, 3 H), 1.22 (s, 3 H), 1.28–1.38 (m, 1 H), 1.69–1.76 (m, 1 H), 1.84 (t, J=12.4 Hz, 1 H), 1.87–1.93 (m, 1 H), 2.27–2.34 (m, 2 H), 2.72 (d, J=10.8 Hz, 1 H), 4.04–4.13 (m, 3 H), 4.16 (d, J=13.9 Hz, 1 H), 5.94 (d, J=13.9 Hz, 1 H), 7.22–7.28 (m, 6 H), 7.32 (d, J=4.0 Hz, 2 H), 7.37 (d, J=7.9 Hz, 1 H) ppm. The resulting mixture was stirred at 0 °C for 15 min and for further 16 h at ambient temperature. C21H29NO3 (343.47 g mol−1). 56(11) (1964) 39. For the preparation of compounds 18 j and 18 k see the Supporting Information. PubMed Google Scholar, Becker, J., Hölderich, W.F. Meta-phenylenediamine has commercial significance as the starting material for dyestuff manufacture and, as the component of a polyamide fiber, Nomex@, marketed by Du Pont. Benzene evaporates into air very quickly and dissolves slightly in water. Your feedback will go directly to Science X editors. Fetching data from CrossRef. Finally, inspired by reports of Buchwald et al.,30 we used K3PO4 as base, and the amount of product 18 a increased (Scheme 5). The ortho isomer has little commercial significance. Therefore, an electrophilic amination reaction i.e. T. Cuypers, T. Morias, S. Windels, C. Marquez, C. Van Goethem, I. Vankelecom and D. E. De Vos, Centre for Membrane Separations, Adsorption, Catalysis and Spectroscopy (cMACS), KU Leuven – University of Leuven, Celestijnenlaan 200F, Post Box 2461, 3001 Heverlee, Belgium, International Symposium on Green Chemistry 2019, Instructions for using Copyright Clearance Center page. Secondly, the ester function was submitted to saponification and the resulting carboxylic acid could be amidated using HATU as coupling reagent to furnish different amides. Then (NH4)2CO3 (269 mg, 2.80 mmol) was added and the reaction mixture was stirred at ambient temperature for 16 h. Subsequently, H2O (5 mL) and MTBE (5 mL) were added and the crude product 27 d precipitated. Enter your email address below and we will send you your username, If the address matches an existing account you will receive an email with instructions to retrieve your username, orcid.org/http://orcid.org/0000-0003-1433-6579, I have read and accept the Wiley Online Library Terms and Conditions of Use. Methyl 8,9,10,10 a‐tetrahydro‐7H‐cyclohepta[b]benzofuran‐10 a‐carboxylate (23 c): According to GPB, β‐oxoester 20 c (105 mg, 279 μmol), K3PO4 (178 mg, 837 μmol) and CuI (8 mg, 0.04 mmol) were converted in benzylamine (0.5 mL) to yield the title compound 23 c (12 mg, 49 μmol, 18 %) after chromatography (SiO2, hexanes/MTBE 20:1, Rf=0.21) as a colorless solid. H. Schulz, M. Schon and N.M. Rahman, in: Stud. This article is part of the themed collection: For reproduction of material from all other RSC journals and books: For reproduction of material from all other RSC journals. 1H NMR (500 MHz, CDCl3): δ=1.15 (t, J=7.1 Hz, 3 H), 1.55 (dddd, J=14.2 Hz, J=12.4 Hz, J=11.1 Hz, J=5.6 Hz, 1 H), 1.77–1.86 (m, 1 H), 1.88–1.97 (m, 2 H), 2.27–2.31 (m, 1 H), 2.46 (dd, J=14.2 Hz, J=4.9 Hz, 1 H), 3.46 (dd, J=11.1 Hz, J=0.8 Hz, 1 H), 3.69 (s, 3 H), 4.11 (q, J=7.1 Hz, 2 H), 4.32 (ddd, J=15.4 Hz, J=6.7 Hz, J=1.1 Hz, 1 H), 4.79 (ddd, J=15.4 Hz, J=6.4 Hz, J=1.4 Hz, 1 H), 5.92 (dt, J=15.7 Hz, J=1.3 Hz, 1 H), 6.97 (dt, J=15.7 Hz, J=6.5 Hz, 1 H), 7.20–7.22 (m, 1 H), 7.28–7.36 (m, 3 H) ppm. This reaction allows you to get the production in one-step route.". The crude product was purified by column chromatography to yield benzazocinones 27 a–27 c. 1‐Benzyl‐2‐oxo‐1,2,3,4,5,6‐hexahydrobenzo[b]azocine‐6‐carboxylic acid N‐[1‐methyl‐1‐(ethoxycarbonyl)ethyl]amide (27 a): According to GPD, HATU (209 mg, 550 μmol), DIPEA (71 mg, 0.55 mmol) and ethyl 2‐aminoisobutyrate (98 mg, 0.75 mmol) were converted with benzazocinone 26 (154 mg, 500 μmol) to yield the title compound 27 a (183 mg, 433 μmol, 87 %) after chromatography (SiO2, hexanes/MTBE 1:7, Rf=0.28) as a colorless oil. The combined organic layers were dried (MgSO4), filtered and the solvent was removed in vacuo. General procedure B (GPB) for the Ullmann type coupling of β‐oxoesters 20 a–20 c with amines: Under exclusion of air and moisture (nitrogen atmosphere), a Schlenk tube was charged with α‐arylated β‐oxoester 20 (1.0 equiv), K3PO4 (2.0–3.0 equiv) and CuI (15 mol %), three times evacuated and flushed with nitrogen. N‐Debenzylation of benzazocinone 18 a: A suspension of 10 % Pd/C (883 mg, 830 μmol) and benzazocinone 18 a (560 mg, 1.66 mmol) in iPrOH (8 mL) was stirred at 50 °C for 2 d under an atmosphere of hydrogen (1 bar). 1H NMR (500 MHz, CDCl3): δ=1.16 (t, J=7.1 Hz, 3 H), 1.57–1.64 (m, 2 H), 1.86–1.90 (m, 1 H), 2.19–2.31 (m, 2 H), 2.83 (dd, J=8.6 Hz, J=3.1 Hz, 1 H), 4.11 (q, J=7.1 Hz, 2 H), 5.31 (t, J=3.8 Hz, 1 H), 6.91–6.96 (m, 2 H), 7.20 (td, J=7.9 Hz, J=1.2 Hz, 1 H), 7.31 (dd, J=7.4 Hz, J=0.8 Hz, 1 H) ppm. THF (2 L mol−1) was added and the resulting mixture was further stirred at −78 °C for 30 min. C19H19NO3 (309.37 g mol−1). The amine (1‐1.8 L mol−1) was then added and the tube was tightly closed. IR (ATR): ṽ=3189 (w), 2945 (w), 1727 (s), 1659 (vs), 1495 (m), 1443 (m), 1390 (m), 1371 (m), 1301 (m), 1222 (m), 1185 (s), 1142 (m), 1096 (m), 1048 (m), 1017 (m), 764 (s), 734 (m) cm−1. Yet, nobody has achieved any results that could be widely applied in practice. All spectroscopic data are in accordance with the literature.25 C14H15IO3 (358.18 g mol−1). For the preparation of compounds 20 b and 20 c see the Supporting Information. Therefore, an electrophilic amination reaction i.e. A team of chemists from Tomsk Polytechnic University discovered a mechanism of direct electrophilic amination and predicted the ways of its implementation. HR‐MS (ESI): calcd 251.1254 (for C15H16LiO3+), found 251.1257 [M+Li+]. XX is the XXth reference in the list of references. Ethyl 1‐(cyclohexylmethyl)‐2‐oxo‐1,2,3,4,5,6‐hexahydrobenzo[b]azocine‐6‐carboxylate (18 h): 1H NMR (500 MHz, CDCl3): δ=1.05–1.19 (m, 4 H), 1.17 (t, J=7.1 Hz, 3 H), 1.51–1.71 (m, 7 H), 1.80–1.86 (m, 3 H), 1.90–1.96 (m, 1 H), 2.23 (dd, J=11.1 Hz, J=8.1 Hz, 1 H), 2.43–2.46 (m, 1 H), 3.22 (dd, J=13.5 Hz, J=5.2 Hz, 1 H), 3.63 (d, J=10.7 Hz, 1 H), 4.06–4.21 (m, 3 H), 7.20–7.22 (m, 1 H), 7.27–7.31 (m, 2 H), 7.33–7.36 (m, 1 H) ppm.

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