N,N-dimethyl-1-naphthylamine compound preparation method

A technology for dimethyl amide and compound, which is applied in the field of preparation of N,N-dimethyl-1-naphthylamine compounds, can solve the problems of harsh reaction conditions, low compound yield, inability to prepare and the like, and achieves reaction operation The effect of simplicity, high product yield and strong compatibility

Active Publication Date: 2019-08-06
HUNAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] At present, some literatures have reported the synthesis method of 1-naphthylamine by benzocyclization amination reaction (Angew.Chem., Int.Ed., 2004, 43, 5694-5697; J.Org.Chem., 2016,81,1696-1703; Tetrahedron 2016,72,4608–4615; J.Organomet.Chem.,2001,634,1;) But none of these methods can prepare N,N-dimethyl-1-naphthylamine compounds , poor substrate compatibility, use of toxic and harmful organic solvents, many reaction steps
The traditional method is to obtain by transition metal-catalyzed coupling reaction between naphthyl halides or halogen-like compounds and dimethylamine, however, these

Method used

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Examples

Experimental program
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Effect test

Synthetic example 1

[0026] Synthesis of N,N-Dimethyl-3-phenylnaphthalene-1-amine

[0027] Add 0.20mmol phenylacetylene, 0.40mmol o-bromoacetophenone, 0.30mmol N,N-dimethylformamide, 0.02mmol cuprous iodide, 0.40mmol sodium hydroxide, and 1.0mL water into the reactor. Under nitrogen atmosphere, heat to 120°C, keep stirring for 22h, stop the reaction, cool to room temperature, add saturated ammonium chloride solution to wash, then extract with ethyl acetate, dry, and distill off the solvent under reduced pressure, the crude product is separated by column chromatography The target product was obtained with a yield of 83%. 1 H NMR (400MHz, CDCl 3 ):δ8.26-8.23(m,1H),7.89-7.86(m,1H),7.74-7.72(m,3H),7.51-7.47(m,4H),7.39(t,J=7.4Hz,1H ), 7.32(s,1H), 2.97(s,6H).

Synthetic example 2

[0029] Synthesis of 3-(4-fluorophenyl)-N,N-dimethylnaphthalene-1-amine

[0030] Add 0.20mmol 4-fluorophenylacetylene, 0.40mmol o-bromoacetophenone, 0.30mmol N,N-dimethylformamide, 0.02mmol cuprous iodide, 0.40mmol sodium hydroxide, and 1.0mL water into the reactor. Under nitrogen atmosphere, heat to 120°C, keep stirring for 24h, stop the reaction, cool to room temperature, add saturated ammonium chloride solution to wash, then extract with ethyl acetate, dry, and distill off the solvent under reduced pressure, the crude product is separated by column chromatography The target product was obtained with a yield of 81%. 1 H NMR (400MHz, CDCl 3 ):δ8.25-8.23(m,1H),7.88-7.86(m,1H),7.69-7.66(m,3H),7.51-7.49(m,2H),7.25(s,1H),7.18(t , J=8.1Hz, 2H), 2.97(s, 6H).

Synthetic example 3

[0032] Synthesis of N,N-Dimethyl-3-(p-tolyl)naphthalene-1-amine

[0033]Add 0.20mmol 4-ethynyltoluene, 0.42mmol o-bromoacetophenone, 0.30mmol N,N-dimethylformamide, 0.04mmol cuprous chloride, 0.40mmol sodium hydroxide, and 1.0mL water into the reactor. Under nitrogen atmosphere, heat to 120°C, keep stirring for 30h, stop the reaction, cool to room temperature, add saturated ammonium chloride solution to wash, then extract with ethyl acetate, dry, and distill off the solvent under reduced pressure, the crude product is separated by column chromatography The target product was obtained with a yield of 89%. 1 H NMR (400MHz, CDCl 3 ):δ8.24-8.22(m,1H),7.87-7.85(m,1H),7.70(s,1H),7.62(d,J=8.1Hz,2H),7.49-7.46(m,2H), 7.31-7.29 (m, 3H), 2.96 (s, 6H), 2.43 (s, 3H).

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Abstract

The invention provides a method for preparing a N,N-dimethyl-1-naphthylamine compound from terminal alkyne, o-bromoacetophenone and a N,N-dimethylamide compound. According to the present invention, the method uses cheap and easily available raw materials and a copper catalyst, and has characteristics of strong functional group compatibility, easy separation of the target product, simple and convenient operation, safety, reliability and high yield of the product; with the method, the problems of low yield, requirement of substrate pre-functionalization, not wide applicability, complex operation, use of ligands, use of precious metals, use of toxic organic solvents, and the like of other synthesis methods are solved; and the method has potential application prospects in fluorescent probes, dyes and bioactive drugs.

Description

[0001] 【Technical field】 [0002] The invention relates to the fields of organic synthesis and pesticide medicine, in particular to a preparation method of N,N-dimethyl-1-naphthylamine compounds. [0003] 【Background technique】 [0004] Naphthylamine is a very important aromatic amine compound, which widely exists in natural products, such as dihydrosanginarine, oxysanginarine, Ancisheynine, etc. Biological activity (Bioorg.Med.Chem.2007,15,1356–1362; Chem.Commun.,2014,50,11314–11316; Org.Lett.,2006,8,1037–1040; J.Med.Chem. , 2003, 46, 5638–5650;). Naphthylamine derivatives are also widely used in pesticides, dyes and functional materials (Org.Lett., 2012, 14, 5385–5387; J.Org.Chem., 2014, 79, 3244–3248; Pharm.Res., 2008 , 25, 1487–1499; Arch. Pharm., 2006, 339, 145–152;). Recently, N,N-dimethyl-1-naphthylamines have attracted the attention of many chemists and biologists, due to the electron-rich nature of its N,N-dimethyl group, through the push-pull on the naphthalene rin...

Claims

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Application Information

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IPC IPC(8): C07C209/60C07C211/57C07C211/59C07C213/02C07C217/94C07D333/20C07D319/22C07B43/04
CPCC07B43/04C07C209/60C07C213/02C07D319/22C07D333/20C07C211/57C07C211/59C07C217/94
Inventor 周永波苏乐斌潘能刘立鑫董建玉尹双凤
Owner HUNAN UNIV
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