Synthetic method for 2-(2-hydroxyphenyl)-2-oxyacetate

A technology of oxyacetate and hydroxyphenyl, which is applied in the field of synthesis of 2--2-oxyacetate, can solve the problems of multiple wastes, difficult separation, difficult control, etc., and achieve simple treatment, easy manipulation, and good reaction conditions mild effect

Active Publication Date: 2015-06-17
常熟市联创化学有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] See the above reaction equation, this method is the most commonly used method for the synthesis of aryl acetone ester, with phenol and ethyl oxalyl chloride in TiCl 4 Under the action of F-C reaction, Lewis acid TiCl 4 The dosage needs to be equal to or in excess of the reactants, it is difficult to recycle after the reaction, and a lot of waste will be generated, which does not meet the requirements of green chemistry
The biggest problem with this reaction is that the para-isomer by-product is produced in the reaction, which is not easy to separate and affects the purity of the product.
[0014] This method uses highly toxic sodium cyanide, the second step needs to be reacted under conditions such as ultra-low temperature, and there are still problems such as low yield of the final product, which all affect the industrial application of this method
[0015] In summary, the methods used are based on aromatic rings as raw materials, and each method has the disadvantage of being difficult to control.

Method used

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  • Synthetic method for 2-(2-hydroxyphenyl)-2-oxyacetate
  • Synthetic method for 2-(2-hydroxyphenyl)-2-oxyacetate
  • Synthetic method for 2-(2-hydroxyphenyl)-2-oxyacetate

Examples

Experimental program
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Effect test

Embodiment 1

[0032] 2-Hydroxy-2-(2'-oxycyclohexyl) ethyl acetate ( III-1 )Synthesis

[0033] Add 1.0 g (4.9 mmol) ethyl glyoxylate ( II-1 , the commercially available quality fraction is 50% II-1 Toluene solution) and 4.8g (49mmol) cyclohexanone ( I ), slowly dropwise added 29 mg (0.25 mmol) of trifluoroacetic acid, stirred at room temperature, concentrated under reduced pressure after 24 h, and the residue was purified by silica gel column chromatography (eluent: the volume ratio of petroleum ether and ethyl acetate was 2:1 ), to get 0.64g product 2-hydroxyl-2-(2'-oxycyclohexanone) ethyl acetate ( III-1 ), light yellow oily liquid, yield 65.4%.

[0034] 1 H NMR (300MHz, CDCl 3 ) δ:4.68(d, J =2.4Hz, 1H), 4.26(q, J =7.1Hz, 2H), 1.87-2.98(m, 10H), 1.29(t, J =7.1Hz, 3H).

Embodiment 2

[0036] 2-(2-Hydroxyphenyl)-2-oxoacetic acid ethyl ester ( IV-1 )Synthesis

[0037] Get 2-hydroxyl-2-(2'-oxycyclohexyl) ethyl acetate ( III-1 ) 200mg (1.0mmol) in a sealed tube, add HIO 3 -DMSO 2.0mL, DMSO 1.0mL, cyclohexene 0.25mL, the reaction device was wrapped with tin foil, stirred at 45°C under temperature control, and monitored by TLC. After 12h, water (10mL) was added to stop the reaction; followed by extraction with ethyl acetate (10mL× 3), combined the ethyl acetate layers, dried over anhydrous sodium sulfate, filtered, and the concentrated residue was purified by column chromatography (eluent: the volume ratio of petroleum ether and ethyl acetate was 10:1); to obtain 116mg Product 2-(2-hydroxyphenyl)-2-oxoacetic acid ethyl ester ( IV-1 ), yellow oily liquid, yield 60.0%.

[0038] 1 H NMR (300MHz, CDCl 3 ) δ: 11.20(s, 1H), 7.70(dd, J 1 =1.5Hz, J 2 =8.0Hz, 1H), 7.61-7.55(m, 1H), 7.04(d, J =8.0Hz, 1H), 7.00-6.94(m, 1H), 4.49(q, J =7.1Hz, 2H), 1.44(t, J ...

Embodiment 3

[0039] Example 3 : Regarding the change in the preparation of ethyl 2-hydroxy-2-(2'-oxocyclohexyl)acetate ( III-1 ) Experimental research on the amount of trifluoroacetic acid in the process

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Abstract

The invention discloses a synthetic method for 2-(2-hydroxyphenyl)-2-oxyacetate. The method comprises the following steps: taking cyclohexanone and glyoxylate as raw materials, producing an Aldol condensation reaction through catalysis at a room temperature, preparing an intermediate 2-hydroxy-2-(2'-oxocyclohexyl)acetate, producing oxidation and dehydro-aromatization reactions through iodic acid-dimethyl sulfoxide, and obtaining 2-(2-hydroxyphenyl)-2-oxyacetate. According to the synthetic method for 2-(2-hydroxyphenyl)-2-oxyacetate, iodic acid is used to produce the dehydro-aromatization reaction for the first time, oxidation and aromatization processes are performed in one step, reagents used in the method are all low in price and easily available, and the method is mild in reaction condition, easy to operate, simple in reaction post-treatment and relatively suitable for large-scale preparation of similar products of 2-(2-hydroxyphenyl)-2-oxyacetate and the like.

Description

technical field [0001] The invention relates to a synthesis method of 2-(2-hydroxyphenyl)-2-oxoacetate, which belongs to the field of synthesis of fine organic intermediates. Background technique [0002] 2-Hydroxyacetophenone, also known as 2-(2-hydroxyphenyl)-2-oxoacetate (IV), belongs to α-ketoester compounds, it is also known as aryl ethyl keto acid Esters are a class of important intermediates with specific structures and functions. Because the α-keto ester molecule contains dual active functional groups: carbonyl group and ester group (or carboxyl group), it has a wide range of applications in the fields of medical treatment, chemical industry and organic synthesis. For example, aryl acetone esters can be reacted with diazo(trimethylsilyl)methylmagnesium bromide (i.e. via Grignard reaction) to generate coumarone derivatives (1)[Hari Y, Kondo R, Date K, et al. Tetrahedron , 2009, 65(42):8708], this kind of compound has anti-cancer, anti-fungal, anti-oxidation and ant...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/313C07C69/738
Inventor 姚其正陈华杨贝贝王永彬张磊
Owner 常熟市联创化学有限公司
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