41317-15-1Relevant articles and documents
Synthesis of 2-methyl-4-methoxydiphenylamine by palladium catalyzed C-N coupling - High synthetic versatility by use of a flexible catalytic system
Scholz, Ulrich,Schlummer, Bj?rn
, p. 6379 - 6385 (2005)
The synthetic versatility of the Buchwald-Hartwig Amination is demonstrated by the synthesis of the industrially important intermediate 2-methyl-4-methoxydiphenylamine. Using four routes differing in the choice of the starting materials, the diarylamine could be synthesized in excellent yields, however, each reaction required a different combination of ligand, base and solvent. This new approach is compared to established industrial routes.
Preparation method of secondary aromatic amine
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Paragraph 0024, (2021/03/31)
The invention provides a method for preparing secondary aromatic amine by performing a palladium-catalyzed C-N coupling reaction on (pseudo)aryl halide and (pseudo)heterocyclic aryl halide and primary(heterocyclic)aromatic amine. The method is characterized in that an alkali for promoting the reaction is an alkali metal carboxylate or an alkali metal bicarbonate.
A terphenyl phosphine as a highly efficient ligand for palladium-catalysed amination of aryl halides with 1° anilines
Shi, Ji-cheng,Zhang, Lixue,Zhou, Fabin
, p. 238 - 243 (2021/09/07)
A terphenyl phosphine ligand (2,6-bis(2,4,6-triisopropylphenyl)phenyl-dicyclohexylphosphine, TXPhos) and its supported palladium complex [(TXPhos)(allyl)PdCl] have been developed and the catalyst system is highly efficient in amination of aryl halides with 1° anilines, especially effective for densely functionalized substrates including both partners possessing ortho-ester, acetyl, nitrile and nitro groups. With the TXPhos-supported catalyst system, many partner combinations have been unprecedentedly realized and the base scope has been even extended to KOAc, which is even the best choice in the amination of 2-nitrochlorobenzene.
Preparation method and application of 2-methyl-4-methoxydiphenylamine
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Paragraph 0070-0098, (2021/06/23)
The invention relates to the field of preparation of diphenylamine, in particular to a preparation method and application of 2-methyl-4-methoxydiphenylamine, and the preparation method of the 2-methyl-4-methoxydiphenylamine comprises the following steps: (1) in a solvent, reacting 2-methyl-4-methoxyaniline with halogenated benzoic acid in the presence of a catalyst and an acid-binding agent to obtain a condensation product, wherein the acid-binding agent is selected from one or more of carbonate, phosphate and hydroxide of alkali metal; (2) acidifying the condensation product, and conducting filtering, washing and drying to obtain a product 1; and (3) decarboxylating the product 1, and conducting purifying to obtain the product 1. The preparation method of the 2-methyl-4-methoxydiphenylamine is convenient to operate, short in time and suitable for large-scale production, and the production efficiency is greatly improved.
Synthesis method of DPA
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Paragraph 0007, (2020/01/25)
The invention discloses a synthesis method of DPA. The method comprises the following steps: (1) adding methanol, o-nitrotoluene, a catalyst, concentrated sulfuric acid, distilled water into an autoclave, performing heating with stirring to 50 DEG C, evacuating air and then introducing hydrogen, controlling a pressure in the autoclave to 0.1 MPa, carrying out a reaction for 5 h, then performing suction filtration, distilling a filtrate to remove methanol, diluting a residual solution by adding water and then adjusting pH to be neutral with ammonia water, performing extracting with toluene, washing an organic phase with a dilute sodium hydroxide solution, and performing reduced pressure distillation on the organic phase to obtain 4-methoxy-2-methylaniline; and (2) adding 4-methoxy-2-methylaniline, phenol naphthalene, cyclohexanone, and the catalyst into an autoclave, replacing air with nitrogen, performing heating to 250 DEG C, controlling a pressure in the autoclave to 1 Mpa, performing cooling to room temperature after a reaction is completed, filtering a reaction solution, and performing reduced pressure distillation on a filtrate and collecting various fractions, wherein a latter fraction is DPA. The raw materials are cheap and easy to obtain, the operation is simple, the yield is high, the energy consumption is low, and the method has practical value and economic value, andis suitable for enterprise production.
Synthetic method of -4- 2- methyl-methoxyl diphenylamine (by machine translation)
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Paragraph 0022-0035, (2019/11/29)
After the reaction is finished, the 2 - organic phase is extracted with DMF toluene, concentrated, vacuum-dried (1) to obtain the intermediate product, (2) and the obtained intermediate product is evaporated and decarboxylated in a methanol system 10~20min 2 - 6~10h 2 . To the synthesis method, the reaction conversion efficiency and selectivity are improved, the raw material conversion rate is improved, the produced process wastewater is less, and the production cost is low. (by machine translation)
Ligand recyclable type method for synthesizing 2-methyl-4-methoxydiphenylamine by catalyzing through copper
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Paragraph 0028; 0108-0109, (2018/07/30)
The invention provides a ligand recyclable type method for synthesizing 2-methyl-4-methoxydiphenylamine by catalyzing through copper. The method takes 2-methyl-4-methoxyaniline and bromobenzene as rawmaterials, an alcohol type compound as a solvent, the copper or a compound of the copper as a catalyst and PSL with a structural formula shown as a formula (I) as a ligand, and the components are subjected to C-N coupling reaction under an alkaline condition at 25 to 120 DEG C, so as to generate the 2-methyl-4-methoxydiphenylamine. The method for synthesizing the 2-methyl-4-methoxydiphenylamine,provided by the invention, has the advantages that reaction conditions are moderate; the green solvent is utilized and is small in environmental pollution; the yield is high, a product is simple to separate and purify and the PSL is easy to recycle; the activity is basically not changed after the ligand is repeatedly used for a plurality of times. The formula (I) is shown in the description.
An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
, p. 3911 - 3920 (2018/09/29)
A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
Preparation method of diphenylamine
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Paragraph 0034; 0037; 0040-0042, (2017/10/12)
The invention relates to a preparation method of diphenylamine, and concretely relates to a preparation method of 2-methyl-4-methoxydiphenylamine. The method comprises the following steps: reacting an initial reaction substance 2-methyl-4-methoxyaniline with halogenated benzoic acid to obtain a carboxyl group-containing diphenylamine compound, and carrying out acidification, decarboxylation and purification to obtain the 2-methyl-4-methoxydiphenylamine.
A method for preparing aromatic amine derivative
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Paragraph 0176-0179, (2016/10/08)
The invention discloses a preparation method of a diarylamine ramification. The preparation method comprises the following steps: dissolving a phenylamine ramification, a phenylhydrazine ramification, a metal phthalocyanine ramification and a copper salt into a solvent, and reacting at -10 to 40 DEG C to obtain the diarylamine ramification. According to the preparation method, the phenylamine ramification and the phenylhydrazine ramification are taken as starting materials, so that raw materials are easy to obtain and plenty in variety; a product obtained by utilizing the method is plenty in type, can not only be directly used, but also be used for other further reactions; and no additive is required to be added. The preparation method disclosed by the invention has the advantages of short synthetic route, moderation in reaction condition, simple reaction operation and post-processing process, high yield and suitability for large-scale production.