Dimethylaminomethylphosphonic Acid Derivatives-Promoted CuI-Catalyzed Synthesis of Aryl Ethers

Ying Jin; Jinyong Liu; Yingwu Yin; Hua Fu; Yuyang Jiang; Yufen Zhao

doi:10.1055/s-2006-941587

LETTER

Dimethylaminomethylphosphonic Acid Derivatives-Promoted CuI-Catalyzed Synthesis of Aryl Ethers

Ying Jin^a, Jinyong Liu^a, Yingwu Yin^a, Hua Fu*^a, Yuyang Jiang^a,b, Yufen Zhao^a
^a Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China
Fax: +86(10)62781695; e-Mail: fuhua@mail.tsinghua.edu.cn;
^b Key Laboratory of Chemical Biology, Guangdong Province, College of Shenzhen, Tsinghua University, Shenzhen 518057, P. R. of China

Abstract

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Abstract

An inexpensive and efficient catalyst system for synthesis of aryl ethers has been developed by using 20 mol% CuI as the catalyst, 30 mol% dimethylaminomethylphosphonic acid derivatives as the new ligands, K₂CO₃ as the base and toluene as the solvent. This is the first example using aminophosphonates as the ligands for Ullmann ether coupling reaction.

Key words

Ullmann reaction - aryl ether - copper-catalyzed - dimethylaminomethylphosphonic acid derivative

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References and Notes

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Synthesis of Diisopropyl Dimethylaminomethyl-phosphonate (L ^¹ ).
The mixed solution of diisopropyl phosphite (22 mmol, 3.7 g), dimethylamine hydrochloride (22 mmol, 1.79 g) and Et₃N (22 mmol, 3.2 mL) in EtOH (30 mL) was added dropwise to 37% aq formaldehyde (1.8 mL), and the resulting solution was refluxed for 8 h. The ³¹P NMR spectroscopy showed that the starting material diisopropyl phosphite was almost quantitatively transferred into ligand L ^¹ (δ = 26.9 ppm). The solvent was removed by rotary evaporation, the residue was isolated by silica gel column chromatography using CHCl₃-MeOH (10:1) as eluent, and the pure L ^¹ was obtained as a colorless liquid. Yield 4.50 g, 92%. ³¹P NMR (121.5 MHz, CDCl₃): δ = 26.9 ppm. ¹H NMR (300 MHz, CDCl₃): δ = 4.78-4.71 (m, 2 H), 2.75 (d, J = 20.4 Hz, 2 H), 1.33 (s, 6 H), 2.41-2.38 (m, 12 H). ¹³C NMR (75 MHz, CDCl₃): δ = 70.2, 56.9, 47.4, 24.0. ESI-HRMS: m/z calcd for C₉H₂₃NO₃P [M + H]⁺: 224.1416; found: 224.1411.
Synthesis of Ethyl Dimethylaminomethylphosphonate (L ^² ).
The mixed solution of diethyl phosphite (22 mmol, 3.0 g), dimethylamine hydrochloride (22 mmol, 1.79 g) in EtOH (30 mL) was added dropwise to 37% aq formaldehyde (1.8 mL), and the resulting solution was refluxed for 6 h. The solvent was removed by rotary evaporation, the residue was dissolved in 5 mL of H₂O and 10 mL of EtOH. Then, LiOH (22 mmol, 0.53 g) was added, and the solution was stirred at 60 °C for 3 h. The solution was extracted with CH₂Cl₂, the aqueous phase was acidified with 3 M HCl to pH 3, and evaporated to dryness to provide a solid mixture. MeOH was added to the remaining solid, and the insoluble solid was filtrated. The filtrate was concentrated and dried over P₂O₅ in vacuo, and the desired product ethyl dimethylamino-methylphosphonate hydrochloride salt (L ^²) was obtained in the form of a white solid. Yield 3.81 g, 85%. ³¹P NMR (121.5 MHz, CDCl₃): δ = 6.8 ppm. ¹H NMR (300 MHz, CDCl₃): δ = 8.98 (s, 1 H), 3.71-3.61 (m, 2 H), 2.80 (d, J = 20.4 Hz, 2 H), 2.59 (s, 6 H), 0.95 (t, J = 7.0 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 60.5, 55.2, 55.3, 45.3, 16.7. ESI-HRMS: m/z calcd for C₅H₁₅NO₃P [M + H]⁺: 168.0790; found: 168.0783.
Synthesis of Dimethylaminomethylphosphonic Acid (L ^³ ).
This compound was synthesized according to the known method.² Dimethylamine hydrochloride (50 mmol, 4.2 g), H₃PO₄ (50 mmol, 4.1 g) and 20 mL of HCl (6.5 M in H₂O) were added to a round-bottom flask fitted with a reflux condenser, and the solution was heated for 5 min. Then, 52 mmol (3.87 mL) of formaldehyde (36% aq solution) was added, and the solution was refluxed for 90 min. After removal of H₂O in vacuo, the residue was heated in 60 mL of EtOH to lead to the formation of a white solid. This solid was collected after filtration, and dried in vacuo to obtain dimethylaminomethyl phosphonic acid hydrochloride salt (L ^³, 8.42 g, 96%). ³¹P NMR (121.5 MHz, DMSO-d ₆,): δ = 9.3 ppm. ¹H NMR (300 MHz, DMSO-d ₆): δ = 5.86 (s, 2 H), 3.30 (d, J = 12.7 Hz, 2 H), 2.83 (s, 6 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 54.7, 52.8, 44.8. ESI-HRMS: m/z calcd for C₃H₁₁NO₃P [M + H]⁺: 140.0477; found: 140.0481.

Characterization data of two representative compounds are shown as follows:
4-Nitrophenyl Phenyl Ether (3j) ⁹
Yellow solid; mp 58-60 °C (Lit.⁷ 60 °C). ¹H NMR (300 MHz, CDCl₃): δ = 8.17 (d, J = 9.27 Hz, 2 H), 7.42 (t, J = 7.89 Hz, 2 H), 7.25 (t, J = 7.56 Hz, 1 H), 7.08 (d, J = 7.82 Hz, 2 H), 7.00 (d, J = 8.85 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 163.5, 154.8, 142.7, 130.4, 126.0, 125.5, 120.6, 117.2. HRMS (EI): m/z calcd for C₁₂H₉NO₃ [M⁺]: 215.0582; found: 215.0574.
Bis(4-methoxyphenenyl)ether (3m) ^5b
White solid; mp 101-103 °C (Lit.^5b 102-103 °C). ¹H NMR (300 MHz, CDCl₃): δ = 6.92 (d, J = 9.27 Hz, 4 H), 6.85 (d, J = 9.27 Hz, 4 H), 3.79 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 155.4, 151.7, 119.6, 114.8, 55.8. HRMS (EI): m/z calcd for C₁₄H₁₄O₃ [M⁺]: 230.0943; found: 230.0949.

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