amination of benzene

https://www.khanacademy.org/.../reactions-benzene/v/bromination-of-benzene (VCH, Weinheim, 1997) p. 374. General procedure D (GPD) for the amide coupling of benzazocinone 26: HATU (1.1 equiv) and DIPEA (1.1–2.2 equiv) were added to a stirred solution of benzazocinone 26 (1.0 equiv) and the primary amine (1.5 equiv) in CH2Cl2 (5 L mol−1) and the resulting mixture was stirred at ambient temperature for 16 h. Subsequently, the mixture was washed with water (1×10 L mol−1), sat. https://doi.org/10.1023/A:1019048526516, DOI: https://doi.org/10.1023/A:1019048526516, Over 10 million scientific documents at your fingertips, Not logged in The first series of derivatizations of the scaffold was initiated by hydrogenolytic debenzylation of N‐benzyl derivative to provide the NH‐congener, which could be deprotonated with LDA and alkylated at nitrogen to give further examples of this compound class. mode) or Thermo Scientific DFS (EI) spectrometers. 1.5 equiv Boc2O, 1.8 equiv pyridine, 1,4‐dioxane, 23 °C, 0.5 h; 2. Working off-campus? XX is the XXth reference in the list of references. The most important was to find a key particle called an intermediate that ensures the formation of the desired product. Get weekly and/or daily updates delivered to your inbox. These materials are the starting point for the synthesis of 6‐carboxybenzo[b]azocin‐2‐ones by a sequence of aryl amination and ring transformation.This reaction sequence starts with copper‐catalyzed formation of N‐alkyl anilines from the iodoarenes and primary … Transformation of β‐oxoesters with PhI(OCOCF3)2 leads to α‐(ortho‐iodophenyl)‐β‐oxoesters. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. 1H NMR (300 MHz, CDCl3): δ=1.24 (t, J=7.1 Hz, 3 H), 1.63–1.80 (m, 1 H), 2.03–2.15 (m, 1 H), 2.44–2.57 (m, 3 H), 3.20 (ddd, J=13.5 Hz, J=9.7 Hz, J=7.0 Hz, 1 H), 4.14–4.30 (m, 2 H), 6.92–6.97 (m, 2 H), 7.28 (td, J=7.8 Hz, J=1.3 Hz, 1 H), 7.93 (dd, J=8.3 Hz, J=1.2 Hz, 1 H) ppm. Learn about our remote access options, Institut für Chemie, Carl von Ossietzky Universität Oldenburg, 26111 Oldenburg, Germany. If you are the author of this article you do not need to formally request permission M.p. IR (ATR): λ−1=3314 (m), 2929 (w), 1717 (s), 1627 (s), 1598 (m), 1521 (m), 1494 (m), 1454 (m), 1447 (m), 1406 (m), 1295 (m), 1247 (s), 1201 (m), 1058 (m), 1025 (m), 911 (m), 906 (m), 759 (m), 734 (s), 702 (s), 626 (m) cm−1. DE19634110 where a reducible metal oxide catalyst in the presence of an oxidant is used to form aniline from benzene. HR‐MS (EI, 70 eV): calcd 247.1203 (for C14H17NO3+), found 247.1196 [M+]. 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. A new method cuts the cost of drug-building chemicals, Amateur astronomer Alberto Caballero finds possible source of Wow! 13C{1H} NMR (125 MHz, CDCl3): δ=14.12 (CH3), 24.27 (CH2), 25.80 (CH2), 26.00 (CH2), 26.25 (CH2), 31.51 (CH2), 31.91 (CH2), 32.16 (CH2), 33.26 (CH2), 36.82 (CH), 44.81 (CH), 55.38 (CH2), 60.91 (CH2), 125.52 (CH), 126.99 (CH), 128.02 (CH), 128.20 (CH), 138.68 (C), 141.46 (C), 173.93 (C), 174.43 (C) ppm. HR‐MS (EI, 70 eV): calcd 315.1829 (for C19H25NO3+), found 315.1835 [M+]. 95–100 °C. Multiplicities of carbon signals were determined with DEPT experiments. We have reported an access to eight‐membered ring lactams by ring transformation of ten different β‐oxoesters 5 with 1,4‐dicarbonyl motif (Scheme 1). 1‐Benzyl‐2‐oxo‐1,2,3,4,5,6‐hexahydrobenzo[b]azocine‐6‐carboxamide (27 d): Pyridine (142 mg, 1.80 mmol) and Boc2O (327 mg, 1.50 mmol) were added to a solution of benzazocinone 26 (309 mg, 1.00 mmol) in 1,4‐dioxane (2 mL) and the resulting mixture was stirred at ambient temperature for 30 min. Ethyl 1‐benzyl‐2‐oxo‐1,2,3,4,5,6‐hexahydrobenzo[b]azocine‐6‐carboxylate (18 a): 1H NMR (500 MHz, CDCl3): δ=1.10 (t, J=7.1 Hz, 3 H), 1.49 (dddd, J=14.1 Hz, J=12.7 Hz, J=11.2 Hz, J=5.6 Hz, 1 H), 1.76–1.85 (m, 1 H), 1.88–1.96 (m, 2 H), 2.30–2.34 (m, 1 H), 2.38 (dd, J=14.1 Hz, J=5.0 Hz, 1 H), 3.20 (dd, J=11.2 Hz, J=0.9 Hz, 1 H), 3.97–4.03 (m, 2 H), 4.68 (d, J=14.0 Hz, 1 H), 5.33 (d, J=14.0 Hz, 1 H), 7.17–7.19 (m, 1 H), 7.22–7.30 (m, 8 H) ppm. It was then coupled with the HATU–DIPEA protocol32 [HATU=O‐(7‐azabenzotriazol‐1‐yl)‐N,N,N′,N′‐tetramethyluronium hexafluorophosphate), DIPEA=ethyldiisopropylamine] with the ethyl esters of aminoisobutyric acid and β‐alanine to give the amides 27 a and 27 b in good yield (87 % and 85 %, respectively). Ethyl 2‐oxo‐1‐prenyl‐1,2,3,4,5,6‐hexahydrobenzo[b]azocine‐6‐carboxylate (18 i): According to GPC, benzazocinone 18 g (124 mg, 500 μmol), nBuLi (0.21 mL, 2.5 mol L−1 in hexanes, 0.53 mmol) and iPr2NH (54 mg, 0.53 mmol) were converted with prenyl bromide (79 mg, 0.53 mmol) to yield the title compound 18 i (119 mg, 377 μmol, 75 %) after chromatography (SiO2, hexanes/MTBE 1:5, Rf=0.43) as a colorless oil. HR‐MS (EI, 70 eV): calcd 308.1519 (for C19H20N2O2+), found 308.1511 [M+]. This reaction allows you to get the production in one-step route.". To appreciate the challenges associated with the amination of two iconic substrates (methane, benzene), suffice it to say that the direct amination of methane and benzene by ammonia to afford methylamine 21 and aniline, 22,23 respectively, (Scheme 2) are both endergonic processes and require a hydrogen scavenger to render them thermodynamically feasible. 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. The mixture was then filtered and the solvent was removed in vacuo. C21H25NO3 (339.44 g mol−1). IR (ATR): ṽ=3318 (m), 3132 (m), 2963 (w), 2928 (w), 1673 (s), 1628 (vs), 1595 (m), 1488 (m), 1450 (m), 1443 (m), 1427 (m), 1411 (m), 1392 (s), 1356 (m), 1333 (m), 1230 (m), 1203 (m), 1157 (m), 1020 (m), 994 (m), 776 (m), 759 (s), 727 (m), 715 (m), 694 (m), 670 (m), 637 (m), 579 (s) cm−1. Arpe, Industrial Organic Chemistry, 3rd Ed. M.p. 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 %). 1H NMR (500 MHz, CDCl3): δ=1.15 (t, J=7.1 Hz, 3 H), 1.46–1.55 (m, 1 H), 1.49 (s, 3 H), 1.61 (s, 3 H), 1.72–1.91 (m, 3 H), 2.21 (dd, J=11.1 Hz, J=7.9 Hz, 1 H), 2.40 (dd, J=13.5 Hz, J=4.7 Hz, 1 H), 3.51 (d, J=11.2 Hz, 1 H), 3.97 (dd, J=14.4 Hz, J=7.3 Hz, 1 H), 4.11 (q, J=7.1 Hz, 2 H), 4.85 (dd, J=14.4 Hz, J=7.3 Hz, 1 H), 5.24 (t, J=7.3 Hz, 1 H), 7.19–7.22 (m, 1 H), 7.24–7.27 (m, 2 H), 7.29–7.32 (m, 1 H) ppm. 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. C14H14O3 (230.26 g mol−1). To help listeners stay abreast of changes, new developments and trends in their industry, IHS Markit experts and analysts have contributed to podcasts on timely and thought-provoking topics. Broaden your knowledge by attending IHS Markit events that feature our subject-matter experts. 13C{1H} NMR (125 MHz, CDCl3): δ=13.98 (CH3), 31.32 (CH2), 37.84 (CH2), 61.40 (CH2), 63.00 (C), 101.56 (CH), 110.74 (CH), 122.51 (CH), 124.81 (CH), 129.03 (C), 129.17 (CH), 161.67 (C), 162.25 (C), 171.76 (C) ppm. With methyl bromoacetate, compound 18 j was obtained in 79 % yield. C19H23NO5 (345.40 g mol−1). M. Gans, Hydrocarbon Proc. ring expansion Sci. C14H17NO3 (247.29 g mol−1).