A Novel Modified Cross-Coupling of Phenols and Amines Using Dichloroimidazolidinedione (DCID)

Abstract

Phenols are considered as an ideal alternative to aryl halides as coupling partners in cross-coupling reactions. In the present work a copper-catalyzed cross-coupling of phenols with various aromatic and aliphatic amines for the synthesis of secondary aryl amines using dichloroimidazolidinedione (DCID) as a new and efficient activating agent has been developed. Substituted phenols were compatible with the standard reaction conditions. The two proposed mechanisms, which are based on the oxidation addition of copper with Ar-OMCID (MCID: Monochloroimidazolidinedione), are also discussed.

Key words

cross-coupling - N-arylation - phenol - amines - dichloroimidazolidinedione - diarylamines

• References and Notes

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• 24 Synthesis of Dichloroimidazolidinedione (DCID, 2) Compound 2 was synthesized by following Gao et al.,¹³ with minor modifications. To N,N′-dicyclohexylcarbodiimine (DCC, 2 g, 1 mmol) in dry dichloromethane (25 mL) at 0 °C was added oxalyl chloride (0.9 mL, 1.05 mmol) dropwise. The reaction mixture was stirred for 1 h at room temperature. The solid material was separated by filtration and washed with cold dichloromethane. The recrystallization of white solid in ethanol yielded DCID (2,5 g, 97%); mp 174–176 °C. ¹HNMR (499.77 MHz, CDCl₃): δ = 3.97–4.00 (m, 2 H), 2.02–2.10 (m, 4 H, Cy), 1.73–1.87 (m, 4 H, Cy), 1.71–1.75 (m, 4 H, Cy), 1.66–1.69 (m, 2 H, Cy), 1.17–1.36 (m, 6 H, Cy) ppm.
• 25 Synthesis of 2-Chloro-1,3-dicyclohexyl-2-phenoxyimidazolidine-4,5-dione (3a) Typically, to an oven-dried 25 mL round-bottom flask containing dry MeCN was added phenol (0.047 g 0.5 mmol) and NaH (0.012 g, 0.5 mmol). The reaction mixture stirred for 30 min at room temperature, and then DCID (0.165 g, 0.5 mmol) was added. The reaction mixture was stirred for 1 h at room temperature and completion of the reaction monitored by TLC. After completion of the reaction salt was filtered, and the filtrate was evaporated under reduced pressure to yield a white solid (0.1 g, 96%). Analytical Data of 2-Chloro-1,3-dicyclohexyl-2-phenoxyimidazolidine-4,5-dione (3a) FTIR: ν = 2929, 2859, 1742, 1399, 1241, 1060 cm^–1. ¹HNMR (499.70 MHz, CDCl₃): δ = 7.16 (t, J = 7.44 Hz, 1 H), 6.82 (t, J = 8.14 Hz, 2 H), 6.76 (d, J = 7.59 Hz, 2 H), 3.95 (m, 1 H), 1.79 (m, 6 H), 1.71 (m, 4 H), 1.65 (m, 2 H), 1.18 (m, 4 H), 1.15 (m, 4 H) ppm. ¹³CNMR (125.66 MHz, CDCl₃): δ = 156.7, 156.2, 128.9, 121.2, 116.3, 114.7, 31.8, 28.9, 28.7, 24.4 ppm. EI-MS: m/z = 393 [M⁺ + 2], 356, 224, 181, 143, 99, 83, 56.
• 26 General Procedure for the One-Pot Cross-Coupling of Phenols and Amines Using DCID Catalyzed by CuI Typically for the synthesis of 5a, to an oven-dried 25 mL round-bottom flask containing dry MeCN (5 mL) were added phenol (1 mmol) and NaH (0.024 g, 1 mmol). The reaction mixture stirred for 30 min at room temperature, and then DCID (0.330 g, 1 mmol) was added. The reaction mixture was stirred for 1 h at room temperature, and completion of the reaction was monitored by TLC. After completion of the reaction, amines (1.6 mmol), Et₃N (0.101 g, 1 mmol), and CuI (0.038 g, 20 mol%) were added, and the reaction mixture was stirred at 80 °C for 24 h (TLC monitoring). For the purification of products, chromatography on silica gel was performed (EtOAc–heptane, 1:3). Structure of the diaryl amines was confirmed by comparison of melting point and NMR spectra reported in the literature (see Supporting Information). Analytical Data of Diphenylamine (5a) White solid; yield: 0.123 g, 73%; mp 52–53°C.^{12c 1}H NMR (499.70 MHz, CDCl₃): δ = 7.92 (d, J = 7.2 Hz, 4 H), 7.52 (t, J = 6.9 Hz, 4 H), 7.48 (m, 2 H), 6.85 (s, 1 H, NH) ppm.
• 27 Scale-Up Synthesis of Diphenylamine (5a) To an oven-dried 250 mL round-bottom flask containing dry MeCN (50 mL) were added phenol (4.7 g, 50 mmol) and NaH (1.2 g, 50 mmol). The reaction mixture was stirred for 30 min at room temperature, and then DCID (16.5 g, 50 mmol) was added. The reaction mixture was stirred for 1 h at room temperature, and completion of the reaction was monitored by TLC. After completion of the reaction aniline (7.23 mL, 80 mmol), Et₃N (6.97 mL, 50 mmol), and CuI (0.19 g, 20 mol%) were added, and the reaction mixture was stirred at 80 °C for 24 h (TLC monitoring). Purification of the product by chromatography on silica gel (EtOAc–heptane, 1:3) yielded compound 5a (6.1 g, 72%).