Synthesis method for ortho amino aromatic formic acid aryl ester derivatives

A technology of amino arylcarboxylic acid and synthesis method, which is applied in the field of chemical synthesis of aryl ortho-amino aryl carboxylic acid derivatives, can solve problems such as poor functional group compatibility, low reaction selectivity, and limitations in promotion, and achieves great practical value. and social and economic benefits, less catalyst dosage, advanced and reasonable process route

Inactive Publication Date: 2014-01-08
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, these two methods usually require the reaction to be carried out under strong acid or basic conditions, and the functional group compatibility of the reaction is not very good
Another method is to use the Baeyer-Villiger oxidative rearrangement reaction (such as Synlett 1999, 462 and Synthesis 1991, 739). The selectivity of this method depends on the difference of the substituents on both sides of the carbonyl group and has high selectivity. However, for the adjacent amino group For aryl formate compounds, the substituents on both sides are aryl groups, so they show similar properties, resulting in extremely low reaction selectivity when the group migrates.
Therefore, the generalization of these methods mentioned above is limited

Method used

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  • Synthesis method for ortho amino aromatic formic acid aryl ester derivatives
  • Synthesis method for ortho amino aromatic formic acid aryl ester derivatives
  • Synthesis method for ortho amino aromatic formic acid aryl ester derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Isatoic anhydride, phenylboronic acid, tris(dibenzylideneacetone) dipalladium, bis(2-diphenylphosphine) phenyl ether, and 1-methylpiperidine are 1.0: 3.0: 0.05: 0.1: 3.0 feed intake, isatoic anhydride 16.3g (0.1mol); phenylboronic acid 36.6g (0.3mol); tris (dibenzylidene acetone) dipalladium 4.58g (0.005mol); bis (2-diphenylphosphine) phenyl ether 5.39g (0.01mol); 29.7g (0.3mol) of 1-methylpiperidine; the organic solvent is tetrahydrofuran 195.6g, and its total amount is 10 times the mass of isatoic anhydride.

[0026] Put isatoic anhydride, phenylboronic acid, tris(dibenzylideneacetone) dipalladium, bis(2-diphenylphosphine) phenyl ether, and 1-methylpiperidine into the reaction kettle, add tetrahydrofuran to dissolve, and the reaction temperature is 60 °C, the reaction was complete after 24 hours.

[0027] After the reaction is over, the organic solvent is reclaimed by distillation under reduced pressure, and the solid remaining in the reaction flask is recrystallized...

Embodiment 2

[0030] Isatoic anhydride, phenylboronic acid, tris(dibenzylideneacetone) dipalladium, tricyclohexylphosphine, triethylamine are 1.0: 3.0: 0.05: 0.1: 3.0 in material ratio, and isatoic anhydride 16.3g (0.1 mol); 36.6g (0.3mol) of phenylboronic acid; 4.58g (0.005mol) of three (dibenzylideneacetone) dipalladium; 2.8g (0.01mol) of tricyclohexylphosphine; 30.4g (0.3mol) of triethylamine; The organic solvent is tetrahydrofuran 163g, and its total consumption is 10 times of the mass of isatoic anhydride.

[0031] All the other are the same as in Example 1, the resulting product phenyl anthranilate 17.7g, yield 83%, purity 98.5%.

Embodiment 3

[0033] Isatoic anhydride, phenylboronic acid, tris(dibenzylideneacetone) dipalladium, bis(2-diphenylphosphine) phenyl ether, and 1-methylpiperidine are 1.0: 3.0: 0.05: 0.1: 3.0 feed intake, isatoic anhydride 16.3g (0.1mol); phenylboronic acid 36.6g (0.3mol); tris (dibenzylidene acetone) dipalladium 4.58g (0.005mol); bis (2-diphenylphosphine) phenyl ether 5.39g (0.01mol); 29.7g (0.3mol) of 1-methylpiperidine; 163g of 1,4-dioxane as the organic solvent, and its total amount is 10 times the mass of isatoic anhydride.

[0034] All the other are the same as in Example 1, the resulting product phenyl anthranilate 14.7g, yield 69%, purity 99.3%.

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Abstract

The invention discloses a synthesis method for ortho amino aromatic formic acid aryl ester derivatives as shown in the constitutional formula (I). The method includes steps of utilizing isatoic anhydride compound as shown in the constitutional formula (II) and aryl boric acid as shown in the constitutional formula (III) as raw materials to sufficiently react in inertial organic solvent in the presence of palladium catalyst, phosphine ligands and alkaline compounds, and then obtaining the ortho amino aromatic formic acid aryl ester derivatives by means of separation and purification of reaction liquid after reaction. The palladium catalyst includes one or a combination of the following palladiums: palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, dichloro-bis (triphenylphosphine) palladium and dichloro-bis (acetylacetonate) palladium. The synthesis method for the ortho amino aromatic formic acid aryl ester derivatives has the advantages of reasonable technology, low toxicity, mild reaction condition, high reaction yield and fine product quality.

Description

(1) Technical field [0001] The invention relates to a chemical synthesis method of an aryl o-aminoarylformate derivative whose structure is shown in formula (I). [0002] (2) Background technology [0003] Aryl anthranilate compounds are a class of compounds with good biological and pharmacological activities, and are widely used in the synthesis of natural products and active drug molecules. Recent studies have shown that this class of compounds also plays an active role in the field of photochemistry. [0004] In the prior art, it is more common to synthesize ortho Aryl amino aryl carboxylate derivatives. However, these two methods usually need to be reacted under strong acid or basic conditions, and the functional group compatibility of the reaction is not very good. Another method is to use the Baeyer-Villiger oxidative rearrangement reaction (such as Synlett 1999, 462 and Synthesis 1991, 739). The selectivity of this method depends on the difference of the substit...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C229/56C07C227/22B01J31/24
Inventor 陈久喜高文霞刘妙昌卢娓吴华悦
Owner WENZHOU UNIVERSITY
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