Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Chiral aromatic amine compounds and preparation method thereof

A technology of amine compounds and aromatic amines, applied in the field of chiral aromatic amine compounds and their preparation, can solve the problems of uneconomical and environmental protection, high toxicity of β-naphthylamine, and large environmental impact

Active Publication Date: 2018-03-20
UNIV OF SCI & TECH OF CHINA
View PDF1 Cites 1 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods are limited to the synthesis of racemic aromatic amine products. There are only a few examples of the synthesis of chiral aromatic compounds through copper-catalyzed oxidative cross-coupling and metal-mediated cross-coupling. The raw materials used are β- Naphthylamine has the disadvantages of high toxicity, great environmental impact, and only racemic products can be obtained, and chiral aromatic amines must be obtained through further chiral resolution
However, in order to obtain optically pure chiral aromatic amine compounds, the resolution of racemates is usually required, which is cumbersome and not economical and environmentally friendly.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Chiral aromatic amine compounds and preparation method thereof
  • Chiral aromatic amine compounds and preparation method thereof
  • Chiral aromatic amine compounds and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Example 1: Preparation of (R)-2'-amino-[1,1'-binaphth]-2-ol (3a)

[0023]

[0024] Under air environment, add 1a (0.2mmol), 2e (0.3mmol), potassium carbonate (0.3mmol), potassium iodide (0.02mmol), dimethyl sulfoxide (2ml) as reaction solvent in reaction tube, in reaction tube After adding a rubber stopper, put it into an oil bath heated to 50°C in advance and stir for 24 hours. Thin-layer chromatography (TLC) spots the plate to determine the end point of the reaction. When the TLC plate shows that the reaction raw material 1a disappears completely, the reaction tube is lifted from the oil bath, and potassium hydroxide (2.0mmol) is directly added to the reaction tube, and then put into The temperature was raised to 150°C in an oil bath and stirred for 4 hours. After the reaction was completed, the reaction tube was cooled to room temperature, and 5 ml of water was added to quench the reaction, then extracted with ethyl acetate and spin-dried, and separated by column ...

Embodiment 2

[0026] Example 2: Preparation of (R)-2'-phenyl-[1,1'-binaphthyl]-2-amine (3b)

[0027]

[0028] Under air environment, add 1b (0.2mmol), 2b (0.3mmol), potassium carbonate (0.3mmol), potassium iodide (0.02mmol), dimethyl sulfoxide (2ml) as reaction solvent in reaction tube, in reaction tube After adding a rubber stopper, put it into an oil bath heated to 50°C in advance and stir for 24 hours. Thin-layer chromatography (TLC) spots the plate to determine the end point of the reaction. When the TLC plate shows that the reaction material 1b disappears completely, the reaction tube is lifted from the oil bath, and sodium hydroxide (6mmol) is directly added to the reaction tube, and then put into the pre- The temperature was raised to 130°C and stirred in an oil bath for 4 hours. After the reaction was completed, the reaction tube was cooled to room temperature, and 5 ml of water was added to quench the reaction, then extracted with ethyl acetate and spin-dried, and separated by c...

Embodiment 3

[0030] Example 3: Preparation of (R)-2'-methyl-[1,1'-binaphthyl]-2-amine (3c)

[0031]

[0032] (R)-2'-methyl-[1,1'-binaphth]-2-ol and 2b were used as the starting substrate of the reaction to prepare the target product 3c, and the preparation method was the same as in Example 2.

[0033] Product yield 96%; yellow solid; 99% ee; 1 H NMR (400MHz, CDCl 3 )δ7.90–7.85(m,2H),7.78(d,J=8.5Hz,2H),7.52(d,J=8.4Hz,1H),7.42–7.36(m,1H),7.25–7.18(m ,3H),7.13(t,J=7.5Hz,1H),7.09(d,J=8.7Hz,1H),6.88(d,J=8.3Hz,1H),3.46(br s,2H),2.13( s,3H). 13 C NMR (101MHz, CDCl 3 )δ141.65,136.15,133.84,132.89,132.73,132.16,129.21,129.04,128.27,128.17,128.15,128.10,126.65,126.53,125.66,125.30,124.11,122.33,118.20,116.37,20.11.ATR-FTIR(cm -1 ):3475,3381,3052,2922,2853,1619,1512,1380,813,746.ESI-MS:calculated[C 21 h 17 N+H] + :284.1433,found:284.1443.[α] 20 D =+5.8 (c=0.96, CH 2 Cl 2 ).HPLC: (OD-H, hexane / i-PrOH=95 / 5, detector: 254nm, flow rate: 1mL / min), t 1 (major)=8.7min,t 2 (minor) = 10.2 min...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses chiral aromatic amine compounds and a preparation method thereof. The chiral aromatic amine compounds are characterized in that under the alkaline condition, compounds I reactwith compounds II to obtain corresponding products, namely chiral aromatic amine compounds labeled by compounds with structural formulas III, IV and V or enantiomers, despinners, diastereoisomers or isotopes thereof: (the formula is shown in the description), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 are separately selected from any group, and X is chlorine or bromine. The chiral aromatic amine compounds with high optical purity (an ee value is greater than 99 percent) have wide application in the fields of bioactivity, materials, chiral ligands, chiral catalysts and the like, and can be further derived to prepare recemic or chiral aromatic amine ligands serving as catalyst for asymmetric catalytic reaction. The invention lays a foundation for developing novel catalysts for the asymmetric catalytic reaction and has economic practicality and industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of preparation methods of aromatic amine compounds in the direction of organic synthesis, and in particular relates to chiral aromatic amine compounds and preparation methods thereof. Background technique [0002] Chiral aromatic amines are important structural units of some natural products, bioactive compounds, materials, chiral ligands and chiral catalysts. In the field of biological activity, natural product compounds such as (-)-streptonigrin (Rao, K.V., Biemann, K. & Woodward R.B.J. Am. Chem. Soc. 1963, 85, 2532-2533), which contain The phenol and arylamine fragments are connected by a special chiral aromatic amine skeleton. This unique structure makes it an antibiotic with significant biological activity. Therefore, this family of compounds has very good anticancer, antibacterial, and fungal properties. , nematodes, viruses and a wide range of biological activities. In the field of catalysis, chiral...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): C07C213/02C07C215/74C07C217/80C07C217/06C07C215/88C07C209/18C07C211/58C07C211/61C07D263/10C07B53/00C07B59/00B01J31/02
CPCB01J31/0235B01J31/0237B01J31/0238C07B53/00C07B59/001C07B59/002C07B2200/05C07B2200/07C07C209/18C07C213/02C07D263/10C07C215/74C07C217/80C07C217/06C07C215/88C07C211/58C07C211/61
Inventor 郭昌常西浩张庆林
Owner UNIV OF SCI & TECH OF CHINA
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com