Chiral 2-imidazoline aniline compound as well as preparation method and application thereof

A technology of imidazoline aniline and compound is applied in the field of chiral catalysts and achieves the effects of mild conditions, simple synthesis method and simple method

Active Publication Date: 2021-07-13
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is still no report on the synthesis and preparation of chiral 2-imidazoline aniline compounds

Method used

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  • Chiral 2-imidazoline aniline compound as well as preparation method and application thereof
  • Chiral 2-imidazoline aniline compound as well as preparation method and application thereof
  • Chiral 2-imidazoline aniline compound as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] (1) Add 16.7g (100mmol) of o-nitrobenzoic acid, 100mL of dichloromethane and 2 drops of N,N-dimethylformamide in a 250mL round bottom flask, slowly add oxalyl chloride (150mmol) dropwise at room temperature, After reacting for 5-8 hours, dichloromethane and excess oxalyl chloride were removed under reduced pressure to obtain o-nitrobenzoyl chloride without purification; the preparation reaction equation is as follows:

[0056]

[0057] (2) Add 0.5151g (5mmol) S-valinol, 20mL dichloromethane and 1.4mL (10mmol) triethylamine into a 100mL round bottom flask, stir well, add 0.6mL (5mmol) o-nitrate under ice bath Base benzoyl chloride, after the addition, was warmed up to room temperature and stirred for 8 hours; the reaction solution was washed with water and saturated brine successively, separated after washing, and the organic phase was dried with anhydrous sodium sulfate, and concentrated to obtain N-[(1S)-2 -Methyl-1-hydroxymethylpropyl]-2-nitrobenzamide (3b), withou...

Embodiment 2

[0064] (1) With step (1) in embodiment 1.

[0065] (2) Same as step (2) in Example 1, wherein the difference is that 0.5151g S-valinol is changed to 0.5948g (5mmol) S-isoleucinol to obtain N-[(1S)-1-isoleucinol Butyl-2-hydroxyethyl]-2-nitrobenzamide crude product (3c), without purification; white solid; the preparation reaction equation is as follows:

[0066]

[0067] (3) With step (3) in embodiment 1, wherein difference is that the crude product of N-[(1S)-2-methyl-1-hydroxymethyl propyl]-2-nitrobenzamide is changed into N -[(1S)-1-Isobutyl-2-hydroxyethyl]-2-nitrobenzamide crude product to give 2-[(4S)-4-isobutyl-N-phenyl-2-imidazole Linyl] nitrobenzene crude product (5c), without purification; the preparation reaction equation is as follows:

[0068]

[0069] (5) Same as step (4) in Example 1, wherein the difference is that the crude product of [(4S)-4-isopropyl-N-phenyl-2-imidazolinyl]nitrobenzene is changed to [(4S) -4-isobutyl-N-phenyl-2-imidazolinyl]nitrobenzen...

Embodiment 3

[0072] (1) With step (1) in embodiment 1.

[0073] (2) With step (2) in embodiment 1, wherein different is that 0.5151g S-valinol is changed into 0.5948g (5mmol) S-secondary leucinol, obtains N-[(1S)-1-secondary Butyl-2-hydroxyethyl]-2-nitrobenzamide crude product (3d), without purification; white solid; the preparation reaction equation is shown in the following formula:

[0074]

[0075] (3) With step (3) in embodiment 1, wherein difference is that the crude product of N-[(1S)-2-methyl-1-hydroxymethyl propyl]-2-nitrobenzamide is changed into N -[(1S)-1-sec-butyl-2-hydroxyethyl]-2-nitrobenzamide crude to give 2-[(4S)-4-sec-butyl-N-phenyl-2-imidazole Linyl] nitrobenzene crude product (5d), without purification; the preparation reaction equation is shown in the following formula:

[0076]

[0077] (4) With step (4) in embodiment 1, wherein difference is that [(4S)-4-isopropyl-N-phenyl-2-imidazolinyl] nitrobenzene crude product is changed into [(4S) -4-sec-butyl-N-pheny...

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Abstract

The invention provides a chiral 2-imidazoline aniline compound as well as a preparation method and application thereof. The preparation method comprises the following steps: reacting an o-nitrobenzoic acid compound as shown in a formula (1), oxalyl chloride and N, N-dimethylformamide to obtain an o-nitrobenzoyl chloride compound as shown in a formula (7); adding the hydroxyl amide derivative into a mixed solution of an amino alcohol compound as shown in a formula (2) and triethylamine to obtain a hydroxyl amide derivative as shown in a formula (3); reacting with thionyl chloride to obtain a dichloro compound as shown in a formula (4); then adding triethylamine and primary amine R2NH2 to prepare a nitroimidazoline derivative; and finally, reducing to obtain the chiral 2-imidazoline aniline compound as shown in a formula (6). The chiral 2-imidazoline aniline compound is easy to prepare, the raw materials are cheap and easy to obtain, the preparation method is simple, and the synthesized chiral ligand containing the 2-imidazoline aniline fragment can be used as a catalyst for catalyzing asymmetric hydroboration reaction of cobalt-catalyzed olefin and asymmetric hydroamination reaction of cobalt-catalyzed non-activated terminal olefin.

Description

technical field [0001] The invention provides a chiral 2-imidazoline aniline compound and its preparation method and application, belonging to the technical field of chiral catalysts Background technique [0002] With the rise of pharmaceuticals, pesticides, materials and other fields, there is an increasing demand for chiral compounds in industry. Among them, the development of new chiral catalysts and their catalytic asymmetric reaction methods as an efficient and direct technology for obtaining chiral compounds has caused attracted extensive attention from the scientific and industrial circles. The key technology in asymmetric catalytic synthesis is to design and synthesize chiral ligand catalysts with high catalytic activity and high stereoselectivity. Judging from the current international research status, the development of chiral catalysts with broad-spectrum catalytic activity and high selectivity is still relatively limited, and most chiral ligands and catalysts wi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D233/24C07D233/20C07D401/12C07D409/12B01J31/22C07B53/00C07F5/02C07C231/18C07C233/65C07C233/66C07C233/73C07C233/18C07D209/14
CPCC07D233/24C07D233/20C07D401/12C07D409/12B01J31/182C07B53/00C07F5/025C07D209/14C07C231/18C07B2200/07B01J2531/845B01J2231/32C07C233/65C07C233/66C07C233/73C07C233/18Y02P20/584
Inventor 陆展沈旭众
Owner ZHEJIANG UNIV
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