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A method for preparing o-alkynyl aniline derivatives

A technology for alkynyl aniline and derivatives, which is applied in the field of preparation of o-alkynyl aniline derivatives, and achieves the effects of simple preparation method, wide application, and cost reduction

Inactive Publication Date: 2016-08-24
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

One-pot synthesis of ortho-alkynylaniline derivatives by reaction of halogenated benzene with O-benzoyl hydroxylamine and acetylenic alcohol catalyzed by palladium phosphine complex and norbornene

Method used

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  • A method for preparing o-alkynyl aniline derivatives
  • A method for preparing o-alkynyl aniline derivatives
  • A method for preparing o-alkynyl aniline derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] In a dry 25 mL Schlenk reaction tube, add 109 mg of o-methyl iodobenzene, 114 mg of benzoyloxymorpholine, 96 mg of 2-methyl-4-phenyl-3-butyn-2-ol, 11 mg palladium acetate, 26 mg of triphenylphosphine, 94 mg of norbornene, 489 mg of cesium carbonate and 2.5 mL of 1,4-dioxane. Under nitrogen protection, stir at 100°C for 18 hours. After the reaction was finished, it was cooled to room temperature and directly passed through a silica gel column (the volume ratio of ethyl acetate to petroleum ether was 1:30) to obtain 133 mg of product with a yield of 96%. The reaction process is shown in the following formula:

[0031]

[0032] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0033] 1 H NMR (400MHz, CDCl 3 ):δ2.52(s,3H),3.24(t,4H),3.93(t,4H),6.81(d,J=8.0Hz,1H),6,93(d,J=7.6Hz,1H) ,7.19(t,J=7.6Hz,1H),7.34-7.38(m,3H),7.52(d,J=7.2Hz,2H); 13 C NMR (100MHz, CDCl 3 ): δ21.29, 51, 99, 67.42, 86.67, 99.57, 115.04, 116.84, 123...

Embodiment 2

[0035] In a dry 25 mL Schlenk reaction tube, add 117 mg of o-methoxyiodobenzene, 114 mg of benzoyloxymorpholine, and 96 mg of 2-methyl-4-phenyl-3-butyn-2-ol , 11 mg of palladium acetate, 26 mg of triphenylphosphine, 94 mg of norbornene, 489 mg of cesium carbonate, and 2.5 mL of 1,4-dioxane. Under nitrogen protection, stir at 100°C for 18 hours. After the reaction was finished, it was cooled to room temperature and directly passed through a silica gel column (the volume ratio of ethyl acetate to petroleum ether was 1:30) to obtain 116 mg of the product with a yield of 79%. The reaction process is shown in the following formula:

[0036]

[0037]Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0038] 1 H NMR (400MHz, CDCl 3 ): δ7.53(d, J=7.6Hz, 2H), 7.33(m, 3H), 7.24(t, J=8.4Hz, 1H), 6.59-6.62(m, 2H), 3.90-3.92(m, 7H), 3.25(t, J=8.0Hz, 4H); 13 C NMR (100MHz, CDCl 3 ): δ161.69, 155.67, 131.35, 129.77, 128.33, 127.99, 123.99...

Embodiment 3

[0040] In a dry 25 mL Schlenk reaction tube, add 127 mg of 1-iodonaphthalene, 114 mg of benzoyloxymorpholine, 96 mg of 2-methyl-4-phenyl-3-butyn-2-ol, 11 mg of palladium acetate, 26 mg of triphenylphosphine, 94 mg of norbornene, 489 mg of cesium carbonate, and 2.5 mL of 1,4-dioxane. Under nitrogen protection, stir at 100°C for 18 hours. After the reaction was finished, it was cooled to room temperature and directly passed through a silica gel column (the volume ratio of ethyl acetate to petroleum ether was 1:30) to obtain 117 mg of product with a yield of 75%. The reaction process is shown in the following formula:

[0041]

[0042] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0043] 1 H NMR (400MHz, CDCl 3 ): δ8.41(d, J=7.6Hz, 1H), 7.79(t, J=8.0Hz, 2H), 7.63(d, J=6.8Hz, 2H), 7.56(t, J=7.6Hz, 1H ),7.35-7.43(m,4H),7.25(s,1H),3.99(d,J=3.6Hz,4H),3.42(d,J=4.0Hz,4H); 13 C NMR (100MHz, CDCl 3 ): δ152.74, 134.80, 131.28, 12...

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Abstract

The invention discloses a method for preparing an o-alkynyl phenylamine derivative. In an organic solvent, reaction of benzene halide, O-benzoyl hydroxylamine and alkynol is catalyzed by a palladium-phosphine complex and norbornene under action of alkaline to synthesize the o-alkynyl phenylamine derivative. According to the preparation method disclosed by the invention, a one-pot process is adopted to directly add benzene halide, hydroxylamine and alkynol into a reaction container by one step, the reaction raw materials are cheap and easily available, the preparation method is simple, and the cost can be greatly reduced by using a little metal palladium as a catalyst. The method disclosed by the invention can be used for synthesizing a series of o-alkynyl phenylamine derivatives; the synthesized product has special ultraviolet absorption characteristics, and can be used for the fields of metal ion detection and coordination chemistry; the o-alkynyl phenylamine is also a raw material for synthesizing heterocyclic compounds of indole and the like and is extensive in use.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of o-alkynyl aniline derivatives catalyzed by palladium acetate and norbornene. Background technique [0002] Due to its special ultraviolet absorption characteristics, o-alkynylaniline derivatives are not only widely used in ion detection and coordination chemistry, but also important intermediates for the synthesis of drugs, so chemists continue to strive to develop o-alkynylaniline-based The novel structure of the backbone and its novel synthetic method. [0003] Ortho-alkynylaniline derivatives can be synthesized from aniline through a series of reactions including ortho-nitration, reduction, diazotization, iodination and Sonogashira coupling (John E.McMurry, Organic Chemistry, Thomson Brooks / Cole Press, Belmont, 2010; J.G Hoggett, R.B.Mppdie, J.R.Penton and K.Schofield, Nitration and Aromatic Reactivity, Cambridge University Press, London, 1997; A.O.Geo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D295/033C07D295/023C07D295/096C07D295/073C07D295/135C07C211/48C07C209/10C07B43/00
Inventor 陈万芝潘善飞
Owner ZHEJIANG UNIV