A One-Pot Approach to 2-(N-Substituted Amino)-1,4-naphthoquinones with Use of Nitro Compounds and 1,4-Naphthoquinones in Water

Xu-Ling Chen; Yu Dong; Shuai He; Rui Zhang; Hua Zhang; Lei Tang; Xiao-Mei Zhang; Ji-Yu Wang

doi:10.1055/s-0037-1610689

Synlett, Table of Contents

Synlett 2019; 30(05): 615-619
DOI: 10.1055/s-0037-1610689

letter

A One-Pot Approach to 2-(N-Substituted Amino)-1,4-naphthoquinones with Use of Nitro Compounds and 1,4-Naphthoquinones in Water

Authors

Xu-Ling Chen

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jiyuwang@cioc.ac.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China
Yu Dong

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jiyuwang@cioc.ac.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China
Shuai He

^cUniversity of the Southwest Minzu, Chengdu 610041, P. R. of China
Rui Zhang

^cUniversity of the Southwest Minzu, Chengdu 610041, P. R. of China
Hua Zhang

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jiyuwang@cioc.ac.cn

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China
Lei Tang

^dLaboratory of Anaesthesia & Critical Care Medicine, Translational Neuroscience Center, and Department of Anaesthesiology, West China Hospital, Sichuan University, Chengdu 610041, P. R. of China
Xiao-Mei Zhang

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jiyuwang@cioc.ac.cn
Ji-Yu Wang*

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jiyuwang@cioc.ac.cn

Abstract

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Abstract

A one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones from 1,4-naphthoquinones and nitro compounds in water has been developed. This method features mild reaction conditions and provides aromatic nitro compounds with various functional groups such as halogens, methylthio, ester, amide, even allyl, propargyl, and heterocycles, as well as aliphatic nitro compounds that are well tolerated. This method can be scaled up and we conducted further transformation of the obtained 2-(N-substituted amino)-1,4-naphthoquinones to synthesize carbazolequinone derivatives.

Key words

amines - 1,4-naphthoquinones - nitro compounds - one-pot reactions - reactions in water - carbazolequinones

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References

References and Notes
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27 Typical Procedure: Preparation of 2-(Phenylamino)naphthalene-1,4-dione (3aa) ²⁵To a solution of 1,4-naphthoquinone (0.3 mmol, 1 equiv), nitrobenzene (0.36 mmol, 1.2 equiv), Zn(OAc)₂ ·2H₂O (0.06 mmol, 20 mol%), Zn (1.5 mmol, 5 equiv) in H₂O (0.6 mL) was added AcOH (4.5 mmol, 15 equiv). The resulting mixture was stirred for 5 h at rt. Then, the reaction mixture was diluted with water, filtered to remove the residual Zn dust, extracted with EtOAc (3×5 mL). The combined organic layers were washed with brine, dried with Na₂SO₄, filtered, and concentrated under reduced pressure. The resulting crude product was then purified by column chromatography (petroleum ether/EtOAc 5:1) on silica gel to afford the desired product as red solid (yield: 93%), mp 184–187 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.21–8.03 (m, 2 H), 7.84–7.70 (m, 1 H), 7.73–7.61 (m, 1 H), 7.57 (s, 1 H), 7.43 (t, J = 7.9 Hz, 2 H), 7.26 (t, J = 7.4 Hz, 3 H), 7.21 (d, J = 7.3 Hz, 1 H), 6.42 (s, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 183.92, 182.05, 144.69, 137.41, 134.91, 133.18, 132.34, 130.34, 129.68, 126.51, 126.14, 125.60, 122.58, 103.36.
28 Reaction on Gram ScaleTo a solution of 1,4-naphthoquinone (1a) (2.3 g, 15 mmol, 1 equiv), 1-methoxy-4-nitrobenzene (2c) (18 mmol, 1.2 equiv), Zn(OAc)₂ ·2H₂O (3 mmol, 20 mol%), Zn (75 mmol, 5 equiv) in H₂O (30 mL) was added AcOH (0.2 mol, 15 equiv). The resulting mixture was stirred for 5 h at rt. Then, the reaction mixture was diluted with water and extracted with EtOAc (3×80 mL). The combined organic layers were washed with brine, dried with Na₂SO₄, filtered, and concentrated under reduced pressure. The resulting crude product was then purified by column chromatography (petroleum ether/EtOAc 5:1) on silica gel to afford the desired product 3ac (yield: 2.9 g, 71%).
29 Synthesis of 2-Methoxy-5H-benzo[b]carbazole-6,11-dione (4ac) ²⁶To a solution of 2-(4-methoxyphenylamino)naphthalene-1,4-dione (3ac) (0.13 g, 0.5 mmol, 1 equiv) in DMF (2.0 mL) were added Pd(OAc)₂ (0.1 mmol, 0.2 equiv) and Cu(OAc)₂ (1.25 mmol, 2.5 equiv). The resulting mixture was stirred for 24 h at 120 °C. Then, the reaction mixture was cooled to rt, diluted with water and extracted with EtOAc (3×20 mL). The combined organic layers were washed with water, brine, dried with Na₂SO₄, filtered, and concentrated under reduced pressure. The resulting crude product was then purified by column chromatography (petroleum ether/EtOAc 1:1) on silica gel to afford the desired product 4ac as a yellow solid (yield: 90.1 mg, 65%), mp 300–305 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 13.00 (s, 1 H), 8.08 (t, J = 7.3 Hz, 2 H), 7.81 (d, J = 19.1 Hz, 2 H), 7.59 (d, J = 2.1 Hz, 1 H), 7.47 (d, J = 9.0 Hz, 1 H), 7.07 (dd, J = 9.0, 2.3 Hz, 1 H), 3.84 (s, 3 H). ¹³C NMR (101 MHz, DMSO-d ₆): δ = 180.06, 177.02, 156.76, 136.82, 133.98, 133.25, 132.96, 132.55, 125.83, 124.65, 118.24, 116.82, 114.80, 101.91, 55.20.

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